Substituted Metallocene Catalysts

ABSTRACT

This invention relates to novel bridged a hafnium transition metal metallocene catalyst compounds having two indenyl ligands substituted at the 4 position, preferably 4 and 7 positions, with a C 1  to C 10  alkyl, where the 2 and 3 positions are hydrogen (assuming the bridge position is counted as the one position) and the bridging atom is carbon or silicon which is incorporated into a cyclic group comprising 3, 4, 5, or 6 silicon and/or carbon atoms that make up the cyclic ring.

STATEMENT OF RELATED CASES

This application is a continuation in part of U.S. Ser. No. 14/325,449,filed Jul. 8, 2014 which claims the benefit of and priority to U.S. Ser.No. 61/847,442, filed Jul. 17, 2013.

This application is also a continuation in part of U.S. Ser. No.14/325,474, filed Jul. 8, 2014 which claims the benefit of and priorityto U.S. Ser. No. 61/847,442, filed Jul. 17, 2013.

FIELD OF THE INVENTION

This invention relates to novel bridged hafnium metallocene compoundscomprising indenyl ligands substituted at the 4 and optionally in the 7positions.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

Catalysts for olefin polymerization are often based on metallocenes ascatalyst precursors, which are activated either with the help of analumoxane, or with an activator containing a non-coordinating anion.

Useful metallocene catalysts have been based upon bis-indenyl transitionmetal compounds. In particular, bridged bis-2-substituted indenyltransition metal compounds and bridged bis-2,4-disubstituted indenyltransition metal compounds have found use in polymerizing propylene, seefor example U.S. Pat. No. 5,276,208 and EP 576 970.

Also see WO 2011/051705 which discloses substituted indenyl compounds,but no cyclic bridging groups. Also see Ransom, et al. Organometallics(2011), 30(4), pp. 800-814 where a series of ansa-bridgedethylene-bis(hexamethylindenyl)zirconium and hafnium complexes wereexplored. Likewise, see CN 2006-10080838 (also referred to as CN101074276 B) which appears to use Me₂Si(2-Me-4-iPrInd)₂HfCl₂ to makeisotactic polypropylene with branching by adding in functionalizedstyrene where the functional group is a vinyl group. See also U.S. Pat.No. 7,741,417; U.S. Pat. No. 7,220,695; and WO 2008/027116 where theprocesses are disclosed to produce isotactic polypropylene by contactingpropylene and optionally one or more monomers with a bis-indenyl Group 4metallocene compound supported on a silica treated with organoaluminumcompound(s) and heterocyclic compound(s), under slurry conditions in thepresence of hydrogen at a temperature of about 50° C. to about 160° C.and a pressure of from about 3 MPa to about 5 MPa to provide a catalystactivity of greater than 30,000 lb of product per lb of catalyst (notethat rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafnium (orzirconium) dimethyl (or dichloride) are listed in the text).

Also see U.S. Pat. No. 7,385,015 where certain bis-indenyl compounds aresupported on a support that has been combined with a firsttrialkylaluminum, calcined, then combined with a second trialkylaluminumcompound(s), where the alkyl groups have two or more carbon atoms andthe first and second trialkylaluminum compound(s) may be the same ordifferent. Note thatrac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafnium (orzirconium) dimethyl (or dichloride) are listed in the text as catalyststhat can be supported and dimethylsilylbis(2-methyl-4-phenyl)hafniumdimethyl is used in the examples.

U.S. Pat. No. 7,220,695 and U.S. Pat. No. 7,741,417 disclose supportedactivators of an ion-exchanged layered silicate, an organoaluminumcompound, and a heterocyclic compound, which may be substituted orunsubstituted. Note thatrac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafnium (orzirconium) dimethyl (or dichloride) are listed in the text as catalyststhat can be supported and dimethylsilylbis(2-methyl-4-phenyl)hafniumdimethyl is used in the examples.

See also “Synthesis and molecular structures of zirconium and hafniumcomplexes bearing dimethylsilandiyl-bis-2,4,6-trimethylindenyl anddimethylsilandiyl-bis-2-methyl-4,6-diisopropylindenyl ligands” Izmer etal., Journal of Organometallic Chemistry (2005), 690(4), pp. 1067-1079which describes zirconium and hafnium ansa-complexes containing2,4,6-trialkyl-substituted indenyl fragments, such as rac- andmeso-Me₂Si(2-Me-4,6-R₂C₉H₃-η⁵)₂MCl₂ (R=Me, iPr; M=Zr, Hf) The complexesreproduced below were disclosed. No polymerizations using thesecompounds were performed.

EP 1 209 165 A2 and U.S. Pat. No. 5,739,366 disclose diphenyl silylbis(4-isopropyl-2,7-dimethylindenyl) ZrCl₂.

U.S. Pat. No. 5,767,033 mentionsdimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}hafniumdichloride at column 11, line 43 and usesrac-dimethylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride and rac-diphenylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconium dichloride in theexamples. Cyclic bridging groups do not appear to be mentioned.

None of the above disclose hafnium based indenyl metallocene compoundswhere the 4 position is substituted, the 2 and 3 positions are notsubstituted, and the bridge is a cyclic group, preferably used incombination with a non-coordinating anion activator.

There is still a need in the art for new and improved catalyst systemsfor the polymerization of olefins, in order to achieve specific polymerproperties, such as high melting point, high molecular weights, toincrease conversion or comonomer incorporation, to alter comonomerdistribution without negatively impacting the resulting polymer'sproperties, increasing vinyl chain ends, particularly increasing vinylunsaturations at the chain end while also maintaining or increasing Mw.

It is therefore an object of the present invention to provide novelcatalyst compounds, catalysts systems comprising such compounds, andprocesses for the polymerization of olefins using such compounds andsystems.

SUMMARY OF THE INVENTION

This invention relates to novel bridged hafnium transition metalmetallocene catalyst compounds having two indenyl ligands substituted atthe 4 position and optionally in the 7 position with a C₁ to C₁₀ alkyl,where the 2 and 3 positions are hydrogen (assuming the bridge positionis counted as the one position) and the bridging atom is carbon orsilicon which is incorporated into a cyclic group comprising 3, 4, 5, or6 silicon and/or carbon atoms that make up the cyclic ring.

This invention relates to a process for producing copolymers comprisingethylene, a cyclic olefin monomer, and optionally one or more C₃ to C₁₂alpha olefins, said process comprising contacting ethylene, a cyclicolefin monomer, and optionally one or more C₃ to C₁₂ alpha-olefins witha catalyst system comprising activator and a metallocene catalystcompound represented by the formula:

where each R³ and R² is hydrogen; each R⁴ is independently a C₁-C₁₀alkyl; each R⁵, R⁶, and R⁷ is independently hydrogen, C₁-C₅₀ substitutedor unsubstituted hydrocarbyl, or C₁-C₅₀ substituted or unsubstitutedhalocarbyl; and R⁴ and R⁵, R⁵ and R⁶, and/or R⁶ and R⁷ may optionally bebonded together to form a ring structure; J is a bridging grouprepresented by the formula R^(a) ₂J, where J is C or Si, and each R^(a)is, independently, C₁ to C₂₀ substituted or unsubstituted hydrocarbyl,and the two R^(a) form a cyclic structure incorporating J and the cyclicstructure may be a saturated or partially saturated cyclic or fused ringsystem; and each X is a univalent anionic ligand, or two Xs are joinedand bound to the metal atom to form a metallocycle ring, or two Xs arejoined to form a chelating ligand, a diene ligand, or an alkylideneligand.

In a preferred embodiment, each R³ and R² is hydrogen, and each R⁴ andR⁷ is independently a C₁-C₁₀ alkyl.

This invention further relates to a catalyst system comprising saidmetallocene catalyst compound(s) and an activator.

This invention further relates to ethylene-cyclic-olefin copolymer andethylene-alpha-olefin-cyclic-olefin copolymer compositions produced bythe methods described herein.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph of polymer Mn vs. calculated wt % ENB for theexperiments in Table 1. Numbers identifying markers correspond to theCat-ID number.

DEFINITIONS

As used herein, the numbering scheme for the Periodic Table Groups isthe new notation as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27(1985). Therefore, a “group 4 metal” is an element from group 4 of thePeriodic Table, e.g., Zr, Ti, and Hf.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group”, “radical”, and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be a radical, which contains hydrogen atoms and up to 50carbon atoms and which may be linear, branched, or cyclic, and whencyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g., F,Cl, Br, I) or halogen-containing group (e.g., CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃ and the like or where at least onenon-carbon atom or group has been inserted within the halocarbyl radicalsuch as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—,═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. Additionally, two or more R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure.

In some embodiments of the invention, the hydrocarbyl radical isindependently selected from methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl,triacontynyl, butadienyl, pentadienyl, hexadienyl, heptadienyl,octadienyl, nonadienyl, and decadienyl. Also included are isomers ofsaturated, partially unsaturated and aromatic cyclic and polycyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl,dipropylphenyl, butylphenyl, dibutylphenyl, benzyl, methylbenzyl,naphthyl, anthracenyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl, norbornyl,norbornenyl, adamantyl and the like. For this disclosure, when a radicalis listed, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl and alkynyl radicals listed include all isomers includingcyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl,1-methylpropyl, tert-butyl, and cyclobutyl (and analogous substitutedcyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (andanalogous substituted cyclobutyls and cyclopropyls); butenyl includes Eand Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls). Cyclic compounds having substitutionsinclude all isomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

For nomenclature purposes, the following numbering schemes are used forindenyl. It should be noted that indenyl can be considered acyclopentadienyl with fused a benzene ring. The structure below is drawnand named as an anion.

The following ring structures are substituted indenyls, where thesubstitution at the 5 and 6 positions forms a ring structure. Forspecific compound nomenclature purposes, these ligands are describedbelow. A similar numbering and nomenclature scheme is used for thesetypes of substituted indenyls that include indacenyls,cyclopenta[b]naphthalenyls, heterocyclopentanaphthyls,heterocyclopentaindenyls, and the like, as illustrated below. Eachstructure is drawn and named as an anion.

Non-limiting examples of indacenyls and cyclopenta[b]naphthalenylsinclude:

Non-limiting examples of heterocyclopentanaphthyls include:

Further non-limiting examples of heterocyclopentanaphthyls includecyclopenta[g]phosphinolyl, cyclopenta[g]isophosphinolyl,cyclopenta[g]arsinolyl, and cyclopenta[g]isoarsinolyl.

Non-limiting examples of heterocyclopentaindenyls include:

Further non-limiting examples of heterocyclopentaindenyls include1-hydrocarbylcyclopenta[f]phosphindolyl,2-hydrocarbylcyclopenta[f]isophosphindolyl,1-hydrocarbylcyclopenta[f]arsindolyl,2-hydrocarbylcyclopenta[f]isoarsindolyl, indeno[5,6-b]selenophenyl,indeno[5,6-b]tellurophenyl, indeno[5,6-c]selenophenyl,indeno[5,6-c]tellurophenyl, 2-hydrocarbylcyclopenta[f]isoindolyl, and1-hydrocarbylcyclopenta[f]indolyl, where hydrocarbyl is a “hydrocarbylradical” as previously defined.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, an indenyl fragment has nine ring carbonatoms. It is within the scope of the invention to replace one of more ofthe ring carbon atoms with a heteroatom, such as a boron atom, a Group14 atom that is not carbon, a Group 15 atom, or a Group 16 atom.Preferred heteroatoms include boron, nitrogen, oxygen, phosphorus, andsulfur.

A “bondable ring position” is a ring position that is capable of bearinga substituent or bridging substituent. For example, indeno[5,6-c]thienylhas seven bondable ring positions (at the carbon atoms) and onenon-bondable ring position (the sulfur atom).

“Ring Structure” means atoms bonded together in one or more cyclicarrangements.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An oligomer is typically a polymerhaving a low molecular weight (such an Mn of less than 25,000 g/mol,preferably less than 2,500 g/mol) or a low number of mer units (such as75 mer units or less). An “ethylene polymer” or “ethylene copolymer” isa polymer or copolymer comprising at least 50 mole % ethylene derivedunits, a “propylene polymer” or “propylene copolymer” is a polymer orcopolymer comprising at least 50 mole % propylene derived units, and soon.

In the context of this document, “homopolymerization” would produce apolymer made from one type of monomer. For example, homopolymerizationof propylene would produce homopolypropylene; homopolymerization ofethylene would produce homopolyethylene; and the like. Likewise,“copolymerization” would produce polymers with more than one monomertype. For example, ethylene copolymers include polymers of ethylene withα-olefins, cyclic olefins and diolefins, vinylaromatic olefins,α-olefinic diolefins, substituted α-olefins, and/or acetylenicallyunsaturated monomers.

Non-limiting examples of α-olefins include propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene,1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene,1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.

For the purposes of this invention, ethylene shall be considered anα-olefin.

Non-limiting examples of cyclic olefins and diolefins (dienes) includecyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,cyclononene, cyclodecene, cyclododecene, norbornene, 4-methylnorbornene,3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclopentene,4-methylcyclopentene, cyclopentadiene, cyclooctadiene,1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,1,4-divinylcyclohexane, 1,5-divinylcyclooctane,1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane,1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, vinylcyclohexene, vinylcyclopentene,vinylcyclobutene, vinylcyclooctene, 5-vinyl-2-norbornene,7,7-dimethyl-bicyclo[2.2.1]hept-2-ene,tricyclo[4.2.1.0^(2,5)]nona-3,7-diene,5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene,methyl-bicyclo[2.2.1]hept-2-ene,2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene,5-ethenylidene-bicyclo[2.2.1]hept-2-ene,5,6-dimethyl-bicyclo[2.2.1]hept-2-ene, and5-ethynyl-bicyclo[2.2.1]hept-2-ene.

Non-limiting examples of vinylaromatic olefins and diolefins includestyrene, para-methylstyrene, para-t-butylstyrene, vinylnaphthylene,vinyltoluene, and divinylbenzene.

Non-limiting examples of α-olefinic dienes include 1,4-hexadiene,1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene,1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene,1,13-tetradecene and 9-methyl-1,9-decadiene.

Substituted α-olefins (also called functional group containingα-olefins) include those containing at least one non-carbon Group 13 to17 atom bound to a carbon atom of the substituted α-olefin where suchsubstitution if silicon may be adjacent to the double bond or terminalto the double bond, or anywhere in between, and where inclusion ofnon-carbon and non-silicon atoms such as for example B, O, S, Se, Te, N,P, Ge, Sn, Pb, As, F, Cl, Br, or I, are contemplated, where suchnon-carbon or non-silicon moieties are sufficiently far removed from thedouble bond so as not to interfere with the coordination polymerizationreaction with the catalyst and so to retain the generally hydrocarbylcharacteristic. By sufficiently far removed from the double bond weintend that the number of carbon atoms, or the number of carbon andsilicon atoms, separating the double bond and the non-carbon ornon-silicon moiety is preferably 6 or greater, e.g., 7, or 8, or 9, or10, or 11, or 12, or 13, or 14 or more. The number of such carbon atoms,or carbon and silicon atoms, is counted from immediately adjacent to thedouble bond to immediately adjacent to the non-carbon or non-siliconmoiety. Examples include allyltrimethylsilane, divinylsilane,8,8,8-trifluoro-1-octene, 8-methoxyoct-1-ene, 8-methylsulfanyloct-1-ene,8-dimethylaminooct-1-ene, or combinations thereof. The use of functionalgroup-containing α-olefins where the functional group is closer to thedouble bond is also within the scope of embodiments of the inventionwhen such olefins may be incorporated in the same manner as are theirα-olefin analogs. See, “Metallocene Catalysts and Borane Reagents in TheBlock/Graft Reactions of Polyolefins”, T. C. Chung, et al, Polym. Mater.Sci. Eng., v. 73, p. 463 (1995), and the masked α-olefin monomers ofU.S. Pat. No. 5,153,282. Such monomers permit the preparation of bothfunctional-group containing copolymers capable of subsequentderivatization, and of functional macromers which may be used as graftand block type polymeric segments.

An α-olefin may also include α-olefinic macromonomers of up to 2000 merunits.

The term “catalyst system” is defined to mean a catalystprecursor/activator pair, and optional co-activator, and an optionalsupport material. When “catalyst system” is used to describe such a pairbefore activation, it means the unactivated catalyst (precatalyst)together with an activator and, optionally, a co-activator. When it isused to describe such a pair after activation, it means the activatedcatalyst and the activator or other charge-balancing moiety. For thepurposes of this invention and the claims thereto, when catalyst systemsare described as comprising neutral stable forms of the components, itis well understood by one of ordinary skill in the art, that the ionicform of the component is the form that reacts with the monomers toproduce polymers.

A transition metal compound may be neutral as in a precatalyst, or acharged species with a counter ion as in an activated catalyst system.

Catalyst precursor is also often referred to as precatalyst, catalyst,catalyst compound, catalyst precursor, transition metal compound ortransition metal complex. These words are used interchangeably.Activator and cocatalyst are also used interchangeably. A scavenger is acompound that is typically added to facilitate oligomerization orpolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments a co-activator canbe pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

A polymerization catalyst system is a catalyst system that canpolymerize monomers to polymer. An “anionic ligand” is a negativelycharged ligand which donates one or more pairs of electrons to a metalion. A “neutral donor ligand” is a neutrally charged ligand whichdonates one or more pairs of electrons to a metal ion.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety such as indenyl) and more frequently two π-boundcyclopentadienyl moieties or substituted cyclopentadienyl moieties.

Non-coordinating anion (NCA) is defined to mean an anion either thatdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. An NCA coordinates weakly enoughthat a neutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center. Any metalor metalloid that can form a compatible, weakly coordinating complex maybe used or contained in the non-coordinating anion. Suitable metalsinclude, but are not limited to, aluminum, gold, and platinum. Suitablemetalloids include, but are not limited to, boron, aluminum, phosphorus,and silicon.

A stoichiometric activator can be either neutral or ionic. The termsionic activator, and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activator,and Lewis acid activator can be used interchangeably.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity index (PDI), is defined to beMw divided by Mn. Unless otherwise noted, all molecular weight units(e.g., Mw, Mn, Mz) are g/mol. The following abbreviations may be usedherein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPris n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu isisobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph isphenyl, Bn or Bz is benzyl, THF or thf is tetrahydrofuran, MAO ismethylalumoxane.

The term “continuous” means a system that operates without interruptionor cessation. For example a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic.

For purposes of this invention, an “alkyl” group is a linear, branched,or cyclic radical of carbon and hydrogen. In a preferred embodiment,“alkyl” refers to linear alkyls.

Room temperature is 22° C., unless otherwise indicated.

DETAILED DESCRIPTION Metallocene Catalyst Compounds

This invention relates to novel bridged a hafnium transition metalmetallocene catalyst compounds having two indenyl ligands substituted atthe 4 position (preferably at the 4 and 7 positions with a C₁ to C₁₀alkyl, where the 2 and 3 positions are hydrogen (assuming the bridgeposition is counted as the one position) and the bridge is carbon orsilicon which is incorporated into a cyclic group comprising 3, 4, 5 or6 silicon and/or carbon atoms that make up the cyclic ring, preferablythe 4, 7 positions, 4, 5, 7 positions, 4, 6, 7 positions, or 4, 5, 6, 7positions are substituted, preferably by a C₁ to C₁₀ alkyl group, andoptionally, if alkyl substituted, the 4 and 5, 5 and 6, and/or 6 and 7positions may be bonded together to form a ring structure.

In a preferred embodiment, this invention is related to metallocenecatalyst compounds, and catalyst systems comprising such compounds,represented by the formula (I):

where each R² and R³ is hydrogen; each R⁴ (preferably each R⁴ and R⁷) isindependently a C₁-C₁₀ alkyl (preferably methyl, ethyl, propyl, butyl,pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomer thereof); eachR⁵, R⁶, and R⁷ are independently hydrogen, or C₁-C₅₀ substituted orunsubstituted hydrocarbyl (preferably hydrogen, methyl, ethyl, propyl,butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomer thereof);and R⁴ and R⁵, R⁵ and R⁶ and/or R⁶ and R⁷ may optionally be bondedtogether to form a ring structure; J is a bridging group represented bythe formula R^(a) ₂J, where J is C or Si, and each R^(a) is,independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl(preferably methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl,nonyl, decyl or an isomer thereof), and two R^(a) form a cyclicstructure incorporating J and the cyclic structure may be a saturated orpartially saturated cyclic or fused ring system; and each X is aunivalent anionic ligand, or two Xs are joined and bound to the metalatom to form a metallocycle ring, or two Xs are joined to form achelating ligand, a diene ligand, or an alkylidene ligand.

In a preferred embodiment of the invention, each R⁴ is, independently, aC₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,heptyl, hexyl, octyl, nonyl, decyl or an isomer thereof, and R⁷ ishydrogen

In a preferred embodiment of the invention, each R⁴ and R⁷ are,independently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof. Each R⁴ and R⁷ may be the same or different.

In a preferred embodiment of the invention, each R⁴, R⁵, and R⁷ are,independently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof. Each, R⁴, R⁵, and R⁷ may be the same or different.

In a preferred embodiment of the invention, each R⁴, R⁶, and R⁷ are,independently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof. Each R⁴, R⁶, and R⁷ may be the same or different.

In a preferred embodiment of the invention, each R⁴, R⁵, R⁶, and R⁷ are,independently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof. Each R⁴, R⁵, R⁶, and R⁷ may be the same or different.

In a preferred embodiment of the invention, each R⁴ and R⁷ are the sameand are selected from the group consisting of C₁ to C₁₀ alkyl group,preferably methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl,nonyl, decyl and isomers thereof.

In a preferred embodiment of the invention, each R⁴ and R⁷ are the sameand are selected from the group consisting of C₁ to C₅ alkyl group,preferably methyl, ethyl, propyl, butyl, pentyl, and isomers thereof.

In a preferred embodiment of the invention, each R⁴ is independently aC₁ to C₄ alkyl group, preferably methyl, ethyl, propyl, butyl andisomers thereof.

In a preferred embodiment of the invention, each R⁴ is independently aC₁ to C₄ alkyl group, preferably methyl, ethyl, n-propyl, cyclopropyl,or n-butyl.

In a preferred embodiment of the invention, each R⁴ and R⁷ are,independently, a C₁ to C₄ alkyl group, preferably methyl, ethyl, propyl,butyl and isomers thereof.

In a preferred embodiment of the invention, each R⁴ and R⁷ are,independently, a C₁ to C₄ alkyl group, preferably methyl, ethyl,n-propyl, cyclopropyl, or n-butyl.

In a preferred embodiment of the invention, each R⁵ and R⁶ areindependently a C₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl,butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomer thereof,and R⁵ and R⁶ may optionally be bonded together to form a substituted orunsubstituted ring structure.

In a preferred embodiment of the invention, each R⁵ and R⁶ areindependently a C₁ to C₅ alkyl group, preferably methyl, ethyl, propyl,butyl, pentyl, or an isomer thereof, and R⁵ and R⁶ may optionally bebonded together to form a substituted or unsubstituted ring structure.

In a preferred embodiment of the invention, each R⁴ is independently aC₁ to C₃ alkyl group, preferably methyl, ethyl, n-propyl, isopropyl orcyclopropyl, each R², R³, R⁵, R⁶, and R⁷ is hydrogen.

In a preferred embodiment of the invention, each R⁴ and R⁷ isindependently a C₁ to C₃ alkyl group, preferably methyl, ethyl,n-propyl, isopropyl or cyclopropyl, each R², R³, R⁵, and R⁶ is hydrogen.

In a preferred embodiment of the invention, each R⁴, R⁵, R⁶ and R⁷ are,independently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof, R² and R³ are hydrogen, and R⁵ and R⁶ are joined together toform a 5-membered ring structure.

In a preferred embodiment of the invention, each R⁴, and R⁷ areindependently methyl, ethyl, or n-propyl, each R⁵ and R⁶ areindependently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof, R² and R³ are hydrogen, and R⁵ and R⁶ are joined together toform a 5-membered ring structure.

In some embodiments of the invention, the 5-membered ring structure hastwo adjacent sp² hybridized carbons with the remaining carbons being sp³hybridized.

In some embodiments of the invention, the 5-membered ring structure hasadditional C₁ to C₁₀ substituents, and wherein the substituents can bethe same or different.

In some embodiments of the invention, the 5-membered ring structure hasadditional C₁ to C₅ substituents, and wherein the substituents can bethe same or different.

In some embodiments of the invention, the 5-membered ring structure hasadditional C₁ to C₁₀ substituents bonded to one or more sp³ hybridizedcarbons, and wherein the substituents can be the same or different.

In some embodiments of the invention, the 5-membered ring structure hasadditional C₁ to C₅ substituents bonded to one or more sp³ hybridizedcarbons, and wherein the substituents can be the same or different.

In a preferred embodiment of the invention, each R⁴, and R⁷ areindependently methyl, ethyl, or n-propyl, each R⁵ and R⁶ areindependently, a C₁ to C₁₀ alkyl group, preferably methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or an isomerthereof, R² and R³ are hydrogen, and R⁵ and R⁶ are joined together toform a substituted 5-membered ring structure.

In a preferred embodiment of the invention, each R⁴ and R⁷ are the sameand are selected from the group consisting of C₁ to C₃ alkyl group,preferably methyl, ethyl, propyl, and isomers thereof, and R², R³, R⁵and R⁶ are hydrogen.

In a preferred embodiment of the invention, J is preferably representedby the formula:

wherein J′ is a carbon or silicon atom, x is 1, 2, 3, or 4, preferably 2or 3, and each R′ is, independently, hydrogen or C₁-C₁₀ hydrocarbyl,preferably hydrogen. Particularly preferred J groups includecyclopentamethylenesilylene, cyclotetramethylenesilylene,cyclotrimethylenesilylene, and the like.

In a preferred embodiment of the invention, each X is, independently,selected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halides, dienes, amines, phosphines, ethers, and a combination thereof,(two X's may form a part of a fused ring or a ring system), preferablyeach X is independently selected from halides and C₁ to C₅ alkyl groups,preferably each X is a methyl, ethyl, propyl, butyl or pentyl group,preferably a methyl group.

In a preferred embodiment of the invention, R⁴ is not an aryl group(substituted or unsubstituted). An aryl group is defined to be a singleor multiple fused ring group where at least on ring is aromatic. Asubstituted aryl group is an aryl group where a hydrogen has beenreplaced by a heteroatom or heteroatom containing group. Examples ofaryl groups include phenyl, benzyl, carbazolyl, naphthyl, and the like.

In a preferred embodiment this invention, R⁴ and R⁷ are not asubstituted or unsubstituted aryl group.

In a preferred embodiment this invention, R⁴, R⁵, R⁶ and R⁷ are not asubstituted or unsubstituted aryl group.

In some embodiments of the invention J may be (R″₂J′)_(k) wherein J′ isindependently carbon or silicon, k is 1, 2, or 3 preferably 1 or 2, andeach R″ is, independently, hydrogen or C₁-C₁₀ hydrocarbyl. Examples of Jinclude dimethylsilylene, methylphenylsilylene, ethylene, methylene andthe like.

In a preferred embodiment of the invention, in Formula (I) each R³ ishydrogen; each R⁴ is independently a C₁-C₁₀ alkyl; each R² isindependently hydrogen; each R⁷ is independently C₁-C₁₀ alkyl; each R⁵and R⁶ is independently hydrogen, C₁-C₅₀ substituted or unsubstitutedhydrocarbyl, or C₁-C₅₀ substituted or unsubstituted halocarbyl; and R⁴and R⁵, R⁵ and R⁶ and/or R⁶ and R⁷ may optionally be bonded together toform a ring structure; J is a bridging group represented by the formulaR^(a) ₂J, where J is C or Si, and each R^(a) is, independently, C₁ toC₂₀ substituted or unsubstituted hydrocarbyl, and the two R^(a) form acyclic structure incorporating J and the cyclic structure may be asaturated or partially saturated cyclic or fused ring system; and each Xis a univalent anionic ligand, or two Xs are joined and bound to themetal atom to form a metallocycle ring, or two Xs are joined to form achelating ligand, a diene ligand, or an alkylidene ligand.

In a preferred embodiment, this invention is related to metallocenecatalyst compounds, and catalyst systems comprising such compounds,represented by the formula (II):

wherein each R² and R³ is hydrogen; R⁴, R⁷, J and X are as definedabove; and each R^(b), R^(c), and R^(d) is independently hydrogen or aC₁ to C₁₀ hydrocarbyl.

In some embodiments of the invention, each R^(b), R^(c), and R^(d) isindependently hydrogen or a C₁ to C₁₀ alkyl.

In some embodiments of the invention, each R^(b), R^(c), and R^(d) isindependently hydrogen or a C₁ to C₅ alkyl.

In some embodiments of the invention, each R^(b), R^(c), and R^(d) isindependently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl or tert-butyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand each R^(c) is independently hydrogen or a C₁ to C₁₀ alkyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand each R^(c) is independently a C₁ to C₁₀ alkyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand each R^(c) is independently hydrogen, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

In some embodiments of the invention, each R^(b), and R^(d) are hydrogenand each R^(c) is independently methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl or tert-butyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand both R^(c) are a C₁ to C₁₀ alkyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand both R^(c) are methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl or tert-butyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand both R^(c)are methyl, ethyl, or n-propyl.

In some embodiments of the invention, each R^(b) and R^(d) is hydrogenand both R^(c) are methyl.

Metallocene compounds that are particularly useful in this inventioninclude one or more of:

-   cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium    dimethyl,-   cyclopentamethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium    dimethyl,-   cyclotrimethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium    dimethyl,-   cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium    dichloride,-   cyclopentamethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium    dichloride,-   cyclotrimethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium    dichloride,-   cyclotetramethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium    dimethyl,-   cyclopentamethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium    dimethyl,-   cyclotrimethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium    dimethyl,-   cyclotetramethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium    dichloride,-   cyclopentamethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium    dichloride,-   cyclotrimethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium    dichloride,-   cyclotetramethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dimethyl,-   cyclopentamethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dimethyl,-   cyclotrimethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dimethyl,-   cyclotetramethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dichloride,-   cyclopentamethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dichloride,-   cyclotrimethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dichloride,-   cyclotetramethylenesilylene-bis(4,8-diethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dimethyl,-   cyclopentamethylenesilylene-bis(4,8-diethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dimethyl,-   cyclotrimethylenesilylene-bis(4,8-diethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dimethyl,-   cyclotetramethylenesilylene-bis(4,8-diethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dichloride,-   cyclopentamethylenesilylene-bis(4,8-diethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dichloride, and-   cyclotrimethylenesilylene-bis(4,8-diethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium    dichloride.

In some embodiments of the invention, useful catalysts include:dimethylsilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,ethylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,dimethylsilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl, and/orethylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl.

In a preferred embodiment, the hafnium dimethyl in any of the compoundslisted above may be replaced with hafnium dialkyl (such as diethyl,dipropyl, diphenyl, dibenzyl) or a dihalide (such as difluoride,dibromide, or diiodide). In a preferred embodiment of the invention, thecatalyst compound is in the rac form. In a preferred embodiment of theinvention, at least 90 wt % of the catalyst compound is in the rac form,based upon the weight of the rac and meso forms present, preferably from92 to 100 wt %, preferably from 95 to 100 wt %, preferably from 98 to100 wt %. In a preferred embodiment of the invention, the ratio of racto meso in the catalyst compound is from 1:100 to 100:1, preferably 1:1to 100:1, preferably 50:1 to 100:1, preferably 85:1 to 100:1. In apreferred embodiment of the invention, the catalyst compound is greaterthan 90% rac, preferably greater than 95% rac, preferably greater than98% rac.

Amounts of rac and meso isomers are determined by proton NMR. ¹H NMRdata are collected at ambient temperature (22° C.) in a 5 mm probe usinga 400 MHz Bruker spectrometer with deuterated solvent in which theprecatalyst compound is completely soluble. Data is recorded using amaximum pulse width of 45°, 8 seconds between pulses and signalaveraging 16 transients.

In a preferred embodiment in any of the processes described herein onemetallocene catalyst compound is used, e.g., the metallocene catalystcompounds are not different. For purposes of this invention onemetallocene catalyst compound is considered different from another ifthey differ by at least one atom. For example “bis-indenyl zirconiumdichloride” is different from (indenyl)(2-methylindenyl) zirconiumdichloride” which is different from “(indenyl)(2-methylindenyl) hafniumdichloride.” Metallocene catalyst compounds that differ only by isomerare considered the same for purposes of determining whether they are the“same”, e.g., rac-dimethylsilylbis(2-methyl-4-propyl)hafnium dimethyland meso-dimethylsilylbis(2-methyl-4-propyl)hafnium dimethyl are isomersof dimethylsilylbis(2-methyl-4-propyl)hafnium dimethyl. Furthermore forhafnium compounds, the Zr analog may be present at up to 3 wt % andstill be considered the “same.” Preferably, the zirconium analog ispresent at less than 2 wt % Zr, more preferably less than 1 wt % Zr,even more preferably less than 0.5 wt % Zr, more preferably less than0.1 wt %. Amount of Zr and Hf present is determined by using ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644).

In some embodiments, two or more different metallocene catalystcompounds are present in the catalyst system used herein. In someembodiments, two or more different metallocene catalyst compounds arepresent in the reaction zone where the process(es) described hereinoccur. When two transition metal compound based catalysts are used inone reactor as a mixed catalyst system, the two transition metalcompounds should be chosen such that the two are compatible. A simplescreening method such as by ¹H or ¹³C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible. It is preferable to use the same activator forthe transition metal compounds, however, two different activators, suchas a non-coordinating anion activator and an alumoxane, can be used incombination. If one or more transition metal compounds contain an Xligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl,then the alumoxane or aluminum alkyl (such as triisobutyl aluminum) aretypically contacted with the transition metal compounds prior toaddition of the non-coordinating anion activator.

The two transition metal compounds (pre-catalysts) may be used in anyratio. Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, andalternatively 5:1 to 50:1. The particular ratio chosen will depend onthe exact pre-catalysts chosen, the method of activation, and the endproduct desired. In a particular embodiment, when using the twopre-catalysts, where both are activated with the same activator, usefulmole percents, based upon the molecular weight of the pre-catalysts, are10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50%B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99%A to 1 to 10% B.

In a preferred embodiment, the hafnium bis-indenyl metallocene compoundused herein is at least 90% rac isomer and is the indenyl groups aresubstituted at the 4 position with a C₁ to C₁₀ alkyl group, the 2 and 3positions are hydrogen, the bridge is carbon or silicon which isincorporated into a 4, 5 or 6 membered ring.

The metallocene compounds described herein are synthesized according toprocedures known in the art.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnon-coordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underpatent number U.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst compound (per metal catalytic site). Theminimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternatepreferred ranges include from 1:1 to 500:1, alternately from 1:1 to200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mole %, alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to a cation or which is only weakly coordinated to acation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible, stabilize the transition metal cation in the sense ofbalancing its ionic charge at +1, and yet retain sufficient lability topermit displacement during polymerization.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides,alkoxy, and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferredare alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and arylgroups having 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, naphthyl, or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. A preferredneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994; all of which are herein fullyincorporated by reference.

Preferred compounds useful as an activator in the process of thisinvention comprise a cation, which is preferably a Bronsted acid capableof donating a proton, and a compatible non-coordinating anion whichanion is relatively large (bulky), capable of stabilizing the activecatalyst species (the Group 4 cation) which is formed when the twocompounds are combined and said anion will be sufficiently labile to bedisplaced by olefinic, diolefinic and acetylenically unsaturatedsubstrates or other neutral Lewis bases, such as ethers, amines, and thelike. Two classes of useful compatible non-coordinating anions have beendisclosed in EP 0 277,003 A1, and EP 0 277,004 A1: 1) anioniccoordination complexes comprising a plurality of lipophilic radicalscovalently coordinated to and shielding a central charge-bearing metalor metalloid core; and 2) anions comprising a plurality of boron atomssuch as carboranes, metallacarboranes, and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and are preferably represented by thefollowing formula (1):

(Z)_(d) ⁺(A^(d−))  (1)

wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewisbase; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe bulky ligand metallocene containing transition metal catalystprecursor, resulting in a cationic transition metal species. Preferably,the activating cation (L-H)_(d) ⁺ is a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

When Z is a reducible Lewis acid it is preferably represented by theformula: (Ar₃C⁺), where Ar is aryl or aryl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl, preferably the reducible Lewis acid is represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl. In a preferred embodiment, the reducible Lewis acid istriphenyl carbenium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6,preferably 3, 4, 5 or 6; n−k=d; M is an element selected from Group 13of the Periodic Table of the Elements, preferably boron or aluminum, andQ is independently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide, and two Q groups may form a ring structure.Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20carbon atoms, more preferably each Q is a fluorinated aryl group, andmost preferably each Q is a pentafluoro aryl group. Examples of suitableA^(d−) components also include diboron compounds as disclosed in U.S.Pat. No. 5,447,895, which is fully incorporated herein by reference.

In a preferred embodiment, this invention relates to a method topolymerize olefins comprising contacting olefins (preferably ethylene)with metallocene catalyst compound described herein, a chain transferagent and a boron containing NCA activator represented by the formula(2):

Z_(d) ⁺(A^(d−))  (2)

where: Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base(as further described above); H is hydrogen; (L-H) is a Bronsted acid(as further described above); A^(d−) is a boron containingnon-coordinating anion having the charge d (as further described above);d is 1, 2, or 3.

In a preferred embodiment in any NCA's represented by Formula 2described above, the reducible Lewis acid is represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ toC₄₀ hydrocarbyl, or a substituted C1 to C40 hydrocarbyl, preferably thereducible Lewis acid is represented by the formula: (Ph₃C⁺), where Ph isphenyl or phenyl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl,or a substituted C₁ to C₄₀ hydrocarbyl.

In a preferred embodiment in any of the NCA's represented by Formula 2described above, Z_(d) ⁺ is represented by the formula: (L-H)_(d) ⁺,wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronstedacid; and d is 1, 2, or 3, preferably (L-H)_(d) ⁺ is a Bronsted acidselected from ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof.

In a preferred embodiment in any of the NCA's represented by Formula 2described above, the anion component A^(d−) is represented by theformula [M*^(k*+)Q*_(n*)]_(d*−) wherein k* is 1, 2, or 3; n* is 1, 2, 3,4, 5, or 6 (preferably 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* isindependently selected from hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbylradicals, said Q* having up to 20 carbon atoms with the proviso that innot more than 1 occurrence is Q* a halide.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene) with a metallocene catalystcompound described herein, a chain transfer agent and an NCA activatorrepresented by the formula (3):

R_(n)M**(ArNHal)_(4-n)  (3)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 3also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, preferably the cation is Z_(d) ⁺ as described above.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula 3 described above, R is selected from the groupconsisting of substituted or unsubstituted C₁ to C₃₀ hydrocarbylaliphatic or aromatic groups, where substituted means that at least onehydrogen on a carbon atom is replaced with a hydrocarbyl, halide,halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid,dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl groups; —SR¹, —NR² ₂, and —PR³₂, where each R¹, R², or R³ is independently a substituted orunsubstituted hydrocarbyl as defined above; or a C₁ to C₃₀ hydrocarbylsubstituted organometalloid.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula 3 described above, the NCA also comprises cationcomprising a reducible Lewis acid represented by the formula: (Ar₃C⁺),where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl, preferably thereducible Lewis acid represented by the formula: (Ph₃C⁺), where Ph isphenyl or phenyl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl,or a substituted C₁ to C₄₀ hydrocarbyl.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula 3 described above, the NCA also comprises acation represented by the formula, (L-H)_(d) ⁺, wherein L is an neutralLewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or3, preferably (L-H)_(d) ⁺ is a Bronsted acid selected from ammoniums,oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879.

Another activator useful herein comprises a salt of a cationic oxidizingagent and a non-coordinating, compatible anion represented by theformula (4):

(OX^(e+))_(d)(A^(d−))_(e)  (4)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Preferred embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

In another embodiment, metallocene catalyst compounds described hereincan be used with Bulky activators. A “Bulky activator” as used hereinrefers to anionic activators represented by the formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group); each R₃ is a halide,C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group ofthe formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl orhydrocarbylsilyl group (preferably R₃ is a fluoride or a C₆perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ can formone or more saturated or unsaturated, substituted or unsubstituted rings(preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic A, alternately greater than300 cubic A, or alternately greater than 500 cubic A.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic A,is calculated using the formula: MV=8.3V_(s), where V_(s) is the scaledvolume. V_(s) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(s) is decreased by 7.5% per fused ring.

Relative Element Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular MV Total Formula of each Per subst. MV Activator Structure ofboron substituents substituent (Å³) (Å³) Dimethylanilinuimtetrakis(perfluoronaphthyl) borate

C₁₀F₇ 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl) borate

C₁₂F₉ 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 515 2060

Exemplary Bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B],and the types disclosed in U.S. Pat. No. 7,297,653.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes of this invention are:

trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropillium tetraphenylborate, triphenylcarbeniumtetraphenylborate, triphenylphosphonium tetraphenylboratetriethylsilylium tetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts, such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,and dicyclohexylammonium tetrakis(pentafluorophenyl)borate; andadditional tri-substituted phosphonium salts, such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Preferred activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄⁻];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(penta-fluorophenyl)borate, (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

In a particularly preferred embodiment, the activator used incombination with any catalyst compound(s) described herein isN,N-dimethylanilinium tetrakis (perfluoronaphthyl)borate.

In a preferred embodiment, any of the activators described herein may bemixed together before or after combination with the catalyst compound,preferably before being mixed with the catalyst compound.

In some embodiments two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In some embodiments, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,preferably 0.1:1 to 1000:1, preferably 1:1 to 100:1.

Further, the typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is a 1:1 molar ratio. Alternate preferredranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1,alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this invention that the catalystcompounds can be combined with combinations of alumoxanes and NCA's (seefor example, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,453,410; EP 0 573120 B1; WO 94/07928, and WO 95/14044 which discuss the use of analumoxane in combination with an ionizing activator).

Optional Scavengers or Co-Activators

In addition to the activator compounds, scavengers or co-activators maybe used. Aluminum alkyl or organoaluminum compounds which may beutilized as scavengers or co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like. Other oxophilicspecies such as diethyl zinc may be used.

Optional Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxides,such as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins, such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeis from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the support material useful in the invention is inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å. In some embodiments, the support materialis a high surface area, amorphous silica (surface area=300 m²/gm; porevolume of 1.65 cm³/gm). Preferred silicas are marketed under thetradenames of DAVISON 952 or DAVISON 955 by the Davison ChemicalDivision of W. R. Grace and Company. In other embodiments DAVISON 948 isused.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce supported catalyst systems of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator. Insome embodiments, the slurry of the support material is first contactedwith the activator for a period of time in the range of from about 0.5hours to about 24 hours, from about 2 hours to about 16 hours, or fromabout 4 hours to about 8 hours. The solution of the metallocene compoundis then contacted with the isolated support/activator. In someembodiments, the supported catalyst system is generated in situ. Inalternate embodiment, the slurry of the support material is firstcontacted with the catalyst compound for a period of time in the rangeof from about 0.5 hours to about 24 hours, from about 2 hours to about16 hours, or from about 4 hours to about 8 hours. The slurry of thesupported metallocene compound is then contacted with the activatorsolution.

The mixture of the metallocene, activator and support is heated to about0° C. to about 70° C., preferably to about 23° C. to about 60° C.,preferably at room temperature. Contact times typically range from about0.5 hours to about 24 hours, from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In embodiments herein, the invention relates to polymerization processeswhere ethylene, the cyclic monomer, and optionally comonomer, arecontacted with a catalyst system comprising an activator and at leastone metallocene compound, as described above. The catalyst compound andactivator may be combined in any order, and are combined typically priorto contacting with the monomer.

Comonomers useful herein include substituted or unsubstituted C₃ to C₄₀alpha olefins, preferably C₃ to C₂₀ alpha olefins, preferably C₃ to C₁₂alpha olefins, preferably propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene and isomers thereof.

Cyclic monomers include C₂ to C₄₀ cyclic monomers (including olefins anddiolefins) may be strained or unstrained, monocyclic or polycyclic, andmay optionally include heteroatoms and/or one or more functional groups.Cyclic monomers may have a single unsaturation such as cyclopentene, ormore than one unsaturation such as norbornadiene.

Useful cyclic monomers include cyclobutene, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclododecene,norbornene, 4-methylnorbornene, 3-methylcyclopentene,4-methylcyclopentene, cyclopentadiene, cyclooctadiene,1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,1,4-divinylcyclohexane, 1,5-divinylcyclooctane,1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane,1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane, norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, vinylcyclohexene, vinylcyclopentene,vinylcyclobutene, vinylcyclooctene, 5-vinyl-2-norbornene,7,7-dimethyl-bicyclo[2.2.1]hept-2-ene,tricyclo[4.2.1.0^(2,5)]nona-3,7-diene,5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene,methyl-bicyclo[2.2.1]hept-2-ene,2,3,3a,4,7,7,7a-hexahydro-4,7-methano-1H-indene,5-ethenylidene-bicyclo[2.2.1]hept-2-ene, 5,6-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethynyl-bicyclo[2.2.1]hept-2-ene,7-oxanorbornene, 7-oxanorbornadiene, and substituted derivativesthereof, and preferably norbornene, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene (ENB), 5-methylidene-2-norbornene,vinylcyclohexene, and 5-vinyl-2-norbornene, most preferably5-ethylidene-2-norbornene.

In some embodiments, the cyclic monomer is preferably a cyclic dienemonomer such as cyclopentadiene, cyclooctadiene, norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, vinylcyclohexene, vinylcyclopentene,vinylcyclobutene, vinylcyclooctene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane, 5-vinyl-2-norbornene,tricyclo[4.2.1.0^(2,5)]nona-3,7-diene, preferably norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene, and5-methylidene-2-norbornene, most preferably 5-ethylidene-2-norbornene.

In another preferred embodiment, the monomer comprises ethylene, one ormore cyclic monomers and an optional comonomers comprising one or moreof propylene or C₄ to C₁₂ olefins. The C₄ to C₁₂ olefin monomers may belinear or branched. In another preferred embodiment, the monomercomprises ethylene, propylene and one or more cyclic monomers.

In another preferred embodiment, the monomer comprises ethylene,propylene and one or more cyclic diene.

In another preferred embodiment, the monomer comprises ethylene,propylene and 5-ethylidene-2-norbornene.

In another preferred embodiment, the monomer comprises ethylene and oneor more cyclic monomers.

In another preferred embodiment, the monomer comprises ethylene andnorbornene.

In a preferred embodiment, one or more cyclic monomers are present inthe polymer produced herein at up to 50 weight %, preferably up to 25weight %, preferably at 2 to 15 weight %, preferably 3 to 12 weight %,even more preferably 6 to 10 weight %, based upon the total weight ofthe composition.

In a preferred embodiment ENB is present in the polymer produced hereinat up to 25 weight %, preferably at 2 to 15 weight %, preferably 3 to 12weight %, even more preferably 6 to 10 weight %, based upon the totalweight of the composition.

In a preferred embodiment of the polymerization process, the conversionof cyclic monomer is greater than 6%, more preferably greater than 10%,more preferably greater than 15%, most preferably greater than 20% basedon the weight of cyclic monomer used in the process and the weight ofcyclic monomer incorporated into the polymer.

In a preferred embodiment of the polymerization process, the conversionof ENB monomer is greater than 6%, more preferably greater than 10%,more preferably greater than 15%, most preferably greater than 20% basedon the weight of ENB used in the process and the weight of ENBincorporated into the polymer.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

When used, preferably the C₃ to C₁₂ alpha-olefins are present in thecopolymer at less than 60 mol %, preferably less than 55 mol %,preferably from 1 to 55 mol %, preferably from 5 to 50 mol %, preferablyfrom 10 to 45 mol %, preferably from 20 to 40 mol %, with the balance ofthe copolymer being made up of ethylene.

Polymerization processes of this invention can be carried out in anymanner known in the art. Any suspension, homogeneous, bulk, solution,slurry, or gas phase polymerization process known in the art can beused. Such processes can be run in a batch, semi-batch, or continuousmode. Homogeneous polymerization processes and slurry processes arepreferred. (A homogeneous polymerization process is defined to be aprocess where at least 90 wt % of the product is soluble in the reactionmedia.) A bulk homogeneous process is particularly preferred. (A bulkprocess is defined to be a process where monomer concentration in allfeeds to the reactor is 70 volume % or more.) Alternately, no solvent ordiluent is present or added in the reaction medium, (except for thesmall amounts used as the carrier for the catalyst system or otheradditives, or amounts typically found with the monomer; e.g., propane inpropylene). In another embodiment, the process is a slurry process. Asused herein the term “slurry polymerization process” means apolymerization process where a supported catalyst is employed andmonomers are polymerized on the supported catalyst particles. At least95 wt % of polymer products derived from the supported catalyst are ingranular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In a preferred embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably less than 0.5 wt %, preferably less than0 wt % based upon the weight of the solvents.

In a preferred embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less,preferably 40 vol % or less, or preferably 20 vol % or less, based onthe total volume of the feedstream. Preferred polymerizations can be runat any temperature and/or pressure suitable to obtain the desiredpolymers. Typical temperatures and/or pressures include a temperature inthe range of from about 0° C. to about 300° C., preferably about 20° C.to about 200° C., preferably about 35° C. to about 150° C., preferablyfrom about 40° C. to about 120° C., preferably from about 45° C. toabout 80° C.; and at a pressure in the range of from about 0.35 MPa toabout 200 MPa, preferably from about 1 MPa to about 70 MPa, orpreferably from about 2 MPa to about 40 MPa, or preferably from about 4MPa to about 20 MPa. In various such embodiments, pressure may rangefrom a low of any one of about 0.1, 1, 5, and 10 to a high of any one ofabout 3, 5, 10, 50, 100, 150, and 200 MPa, provided the high end of therange is greater than the low end.

In a typical polymerization, the run time of the reaction is up to 300minutes, preferably in the range of from about 5 to 250 minutes, orpreferably from about 10 to 120 minutes.

In a some embodiments hydrogen is present in the polymerization reactor.When present, hydrogen is present at a partial pressure of 0.001 to 50psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa).

In an alternate embodiment, the activity of the catalyst is at least 50g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr, preferably 100,000 ormore g/mmol/hr. In an alternate embodiment, the conversion of olefinmonomer is at least 10%, based upon polymer yield and the weight of themonomer entering the reaction zone, preferably 20% or more, preferably30% or more, preferably 50% or more, preferably 80% or more.

In an embodiment of the invention, little or no alumoxane is used in theprocess to produce the polymers. Preferably, alumoxane is present atzero mol %, alternately the alumoxane is present at a molar ratio ofaluminum to transition metal 500:1 or less, preferably 300:1 or less,preferably 100:1 or less.

In an embodiment of the invention, little or no scavenger is used in theprocess to produce the polymer. The scavenger may be present at a molarratio of scavenger metal to transition metal of less than 100:1,preferably less than 50:1, preferably less than 20:1, preferably lessthan 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (preferably 25 to 150° C., preferably 40 to130° C., preferably 70 to 120° C.); 2) is conducted at a pressure ofatmospheric pressure to 40 MPa (preferably 0.35 to 16 MPa, preferablyfrom 0.45 to 12 MPa, preferably from 0.5 to 20 MPa); 3) is conducted inan aliphatic hydrocarbon solvent (such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; preferably where aromatics are preferably present in thesolvent at less than 1 wt %, preferably less than 0.5 wt %, preferablyat 0 wt % based upon the weight of the solvents) or aromatic solventssuch as toluene, benzene or xylenes; 4) wherein the catalyst system usedin the polymerization comprises less than 0.5 mol %, preferably 0 mol %alumoxane, alternately the alumoxane is present at a molar ratio ofaluminum to transition metal 500:1 or less, preferably 300:1 or less,preferably 100:1 or less,) the polymerization preferably occurs in onereaction zone; 5) the productivity of the catalyst compound is at least80,000 g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably atleast 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr); 6)optionally scavengers (such as trialkyl aluminum compounds) are absent(e.g., present at zero mol %, alternately the scavenger is present at amolar ratio of scavenger metal to transition metal of less than 100:1,preferably less than 50:1, preferably less than 20:1, preferably lessthan 10:1); and 7) optionally hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa)(preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa)). In a preferred embodiment, the catalystsystem used in the polymerization comprises no more than one catalystcompound. A “reaction zone” also referred to as a “polymerization zone”is a vessel where polymerization takes place, for example a batchreactor. When multiple reactors are used in either series or parallelconfiguration, each reactor is considered as a separate polymerizationzone. For a multi-stage polymerization in both a batch reactor and acontinuous reactor, each polymerization stage is considered as aseparate polymerization zone. In a preferred embodiment, thepolymerization occurs in one reaction zone. Room temperature is 23° C.unless otherwise noted.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

In a preferred embodiment of the invention, higher reactor temperatures,such as 70 to 150° C., and Bulky activators, such N,N-dimethylaniliniumtetrakis (perfluoronaphthyl)borate are used.

In a preferred embodiment of the invention, the polymerization occurs ina supercritical or supersolution state.

The terms “dense fluid” “solid-fluid phase transition temperature”“phase transition” “solid-fluid phase transition pressure” “fluid-fluidphase transition pressure” “fluid-fluid phase transition temperature”“cloud point” “cloud point pressure” “cloud point temperature”“supercritical state” “critical temperature (Tc)” “critical pressure(Pc)” “supercritical polymerization” “homogeneous polymerization”“homogeneous polymerization system” are defined in U.S. Pat. No.7,812,104, which is incorporated by reference herein.

A supercritical polymerization means a polymerization process in whichthe polymerization system is in a dense (i.e. its density is 300 kg/m³or higher), supercritical state.

A super solution polymerization or supersolution polymerization systemis one where the polymerization occurs at a temperature of 65° C. to150° C. and a pressure of between 250 to 5,000 psi (1.72 to 34.5 MPa),preferably the super solution polymerization polymerizes a C₂ to C₂₀monomer (preferably propylene), and has: 1) 0 to 20 wt % of one or morecomonomers (based upon the weight of all monomers and comonomers presentin the feed) selected from the group consisting of ethylene and C₄ toC₁₂ olefins and diolefins, 2) from 20 to 65 wt % diluent or solvent,based upon the total weight of feeds to the polymerization reactor, 3) 0to 5 wt % scavenger, based upon the total weight of feeds to thepolymerization reactor, 4) the olefin monomers and any comonomers arepresent in the polymerization system at 15 wt % or more, 5) thepolymerization temperature is above the solid-fluid phase transitiontemperature of the polymerization system and above a pressure greaterthan 1 MPa below the cloud point pressure of the polymerization system,provided however that the polymerization occurs: (1) at a temperaturebelow the critical temperature of the polymerization system, or (2) at apressure below the critical pressure of the polymerization system.

In a preferred embodiment of the invention, the polymerization processis conducted under homogeneous (such as solution, supersolution, orsupercritical) conditions preferably including a temperature of about60° C. to about 200° C., preferably for 65° C. to 195° C., preferablyfor 90° C. to 190° C., preferably from greater than 100° C. to about180° C., such as 105° C. to 170° C., preferably from about 110° C. toabout 160° C. The process may conducted at a pressure in excess of 1.7MPa, especially under supersolution conditions including a pressure ofbetween 1.7 MPa and 30 MPa, or especially under supercritical conditionsincluding a pressure of between 15 MPa and 1500 MPa, especially when themonomer composition comprises propylene or a mixture of propylene withat least one ethylene or C₄ to C₂₀ α-olefin. In a preferred embodimentthe monomer is propylene and the propylene is present at 15 wt % or morein the polymerization system, preferably at 20 wt % or more, preferablyat 30 wt % or more, preferably at 40 wt % or more, preferably at 50 wt %or more, preferably at 60 wt % or more, preferably at 70 wt % or more,preferably 80 wt % or more. In an alternate embodiment, the monomer andany comonomer present are present at 15 wt % or more in thepolymerization system, preferably at 20 wt % or more, preferably at 30wt % or more, preferably at 40 wt % or more, preferably at 50 wt % ormore, preferably at 60 wt % or more, preferably at 70 wt % or more,preferably 80 wt % or more.

In a preferred embodiment of the invention, the polymerization processis conducted under supersolution conditions including temperatures fromabout 65° C. to about 150° C., preferably from about 75° C. to about140° C., preferably from about 90° C. to about 140° C., more preferablyfrom about 100° C. to about 140° C., and pressures of between 1.72 MPaand 35 MPa, preferably between 5 and 30 MPa.

In another particular embodiment of the invention, the polymerizationprocess is conducted under supercritical conditions (preferablyhomogeneous supercritical conditions, e.g., above the supercriticalpoint and above the cloud point) including temperatures from about 90°C. to about 200° C., and pressures of between 15 MPa and 1500 MPa,preferably between 20 MPa and 140 MPa.

In another embodiment, the polymerization occurs at a temperature abovethe solid-fluid phase transition temperature of the polymerizationsystem and a pressure no lower than 10 MPa below the cloud pointpressure (CPP) of the polymerization system (preferably no lower than 8MPa below the CPP, preferably no lower than 6 MPa below the CPP,preferably no lower than 4 MPa below the CPP, preferably no lower than 2MPa below the CPP). Preferably, the polymerization occurs at atemperature and pressure above the solid-fluid phase transitiontemperature and pressure of the polymerization system and, preferablyabove the fluid-fluid phase transition temperature and pressure of thepolymerization system.

In an alternate embodiment, the polymerization occurs at a temperatureabove the solid-fluid phase transition temperature of the polymerizationsystem and a pressure greater than 1 MPa below the cloud point pressure(CPP) of the polymerization system (preferably greater than 0.5 MPabelow the CPP, preferably greater than the CCP), and the polymerizationoccurs: (1) at a temperature below the critical temperature of thepolymerization system, or (2) at a pressure below the critical pressureof the polymerization system, preferably the polymerization occurs at apressure and temperature below the critical point of the polymerizationsystem, most preferably the polymerization occurs: (1) at a temperaturebelow the critical temperature of the polymerization system, and (2) ata pressure below the critical pressure of the polymerization system.

Alternately, the polymerization occurs at a temperature and pressureabove the solid-fluid phase transition temperature and pressure of thepolymerization system. Alternately, the polymerization occurs at atemperature and pressure above the fluid-fluid phase transitiontemperature and pressure of the polymerization system. Alternately, thepolymerization occurs at a temperature and pressure below thefluid-fluid phase transition temperature and pressure of thepolymerization system.

In another embodiment, the polymerization system is preferably ahomogeneous, single phase polymerization system, preferably ahomogeneous dense fluid polymerization system.

In another embodiment, the reaction temperature is preferably below thecritical temperature of the polymerization system. Preferably, thetemperature is above the solid-fluid phase transition temperature of thepolymer-containing fluid reaction medium at the reactor pressure or atleast 5° C. above the solid-fluid phase transition temperature of thepolymer-containing fluid reaction medium at the reactor pressure, or atleast 10° C. above the solid-fluid phase transformation point of thepolymer-containing fluid reaction medium at the reactor pressure. Inanother embodiment, the temperature is above the cloud point of thesingle-phase fluid reaction medium at the reactor pressure, or 2° C. ormore above the cloud point of the fluid reaction medium at the reactorpressure. In yet another embodiment, the temperature is between 60° C.and 150° C., between 60° C. and 140° C., between 70° C. and 130° C., orbetween 80° C. and 130° C. In one embodiment, the temperature is above60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C., 95° C., 100° C.,105° C., or 110° C. In another embodiment, the temperature is below 150°C., 140° C., 130° C., or 120° C. In another embodiment, the cloud pointtemperature is below the supercritical temperature of the polymerizationsystem or between 70° C. and 150° C.

In another embodiment, the polymerization occurs at a temperature andpressure above the solid-fluid phase transition temperature of thepolymerization system, preferably the polymerization occurs at atemperature at least 5° C. higher (preferably at least 10° C. higher,preferably at least 20° C. higher) than the solid-fluid phase transitiontemperature and at a pressure at least 2 MPa higher (preferably at least5 MPa higher, preferably at least 10 MPa higher) than the cloud pointpressure of the polymerization system. In a preferred embodiment, thepolymerization occurs at a pressure above the fluid-fluid phasetransition pressure of the polymerization system (preferably at least 2MPa higher, preferably at least 5 MPa higher, preferably at least 10 MPahigher than the fluid-fluid phase transition pressure). Alternately, thepolymerization occurs at a temperature at least 5° C. higher (preferablyat least 10° C. higher, preferably at least 20° C. higher) than thesolid-fluid phase transition temperature and at a pressure higher than,(preferably at least 2 MPa higher, preferably at least 5 MPa higher,preferably at least 10 MPa higher) than the fluid-fluid phase transitionpressure of the polymerization system.

In another embodiment, the polymerization occurs at a temperature abovethe solid-fluid phase transition temperature of the polymer-containingfluid reaction medium at the reactor pressure, preferably at least 5° C.above the solid-fluid phase transition temperature of thepolymer-containing fluid reaction medium at the reactor pressure, orpreferably at least 10° C. above the solid-fluid phase transformationpoint of the polymer-containing fluid reaction medium at the reactorpressure.

In another useful embodiment, the polymerization occurs at a temperatureabove the cloud point of the single-phase fluid reaction medium at thereactor pressure, more preferably 2° C. or more (preferably 5° C. ormore, preferably 10° C. or more, preferably 30° C. or more) above thecloud point of the fluid reaction medium at the reactor pressure.Alternately, in another useful embodiment, the polymerization occurs ata temperature above the cloud point of the polymerization system at thereactor pressure, more preferably 2° C. or more (preferably 5° C. ormore, preferably 10° C. or more, preferably 30° C. or more) above thecloud point of the polymerization system.

In another embodiment, the polymerization process temperature is abovethe solid-fluid phase transition temperature of the polymer-containingfluid polymerization system at the reactor pressure, or at least 2° C.above the solid-fluid phase transition temperature of thepolymer-containing fluid polymerization system at the reactor pressure,or at least 5° C. above the solid-fluid phase transition temperature ofthe polymer-containing fluid polymerization at the reactor pressure, orat least 10° C. above the solid-fluid phase transformation point of thepolymer-containing fluid polymerization system at the reactor pressure.In another embodiment, the polymerization process temperature should beabove the cloud point of the single-phase fluid polymerization system atthe reactor pressure, or 2° C. or more above the cloud point of thefluid polymerization system at the reactor pressure. In still anotherembodiment, the polymerization process temperature is between 50° C. and350° C., or between 60° C. and 250° C., or between 70° C. and 250° C.,or between 80° C. and 250° C. Exemplary lower polymerization temperaturelimits are 50° C., or 60° C., or 70° C., or 80° C., or 90° C., or 95°C., or 100° C., or 110° C., or 120° C. Exemplary upper polymerizationtemperature limits are 350° C., or 250° C., or 240° C., or 230° C., or220° C., or 210° C., or 200° C.

Polyolefin Products

This invention also relates to compositions of matter produced by themethods described herein.

In a preferred embodiment of the invention, the process described hereinproduces ethylene copolymers, such as ethylene-alpha-olefin (preferablyC₃ to C₂₀)-cyclic monomer (preferably cyclic diene monomers) copolymers(such as ethylene-propylene-cyclic monomer copolymers,ethylene-hexene-cyclic monomer copolymers, or ethylene-octene-cyclicmonomer copolymers having: a Mw/Mn of greater than 1 to 4 (preferablygreater than 1 to 3).

In a preferred embodiment of the invention, the process described hereinproduces ethylene copolymers, such as ethylene-alpha-olefin (preferablyC₃ to C₂₀)-cyclic diene copolymers (such as ethylene-propylene-cyclicdiene copolymers, ethylene-hexene-cyclic diene copolymers, orethylene-octene-cyclic diene copolymers having: a Mw/Mn of greater than1 to 4 (preferably greater than 1 to 3).

In a preferred embodiment of the invention, the process described hereinproduces ethylene-propylene-cyclic diene copolymers (such asethylene-propylene-5-ethylidene-2-norbornene copolymers,ethylene-propylene-norbornadiene copolymers orethylene-propylene-5-vinyl-2-norbornene copolymers) having: a Mw/Mn ofgreater than 1 to 4 (preferably greater than 1 to 3).

Non-limiting examples of cyclic olefin monomers (including cyclicdienes, also referred to as cyclic diolefins) useful herein includecyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,cyclononene, cyclodecene, cyclododecene, norbornene, 4-methylnorbornene,3-methylcyclopentene, 4-methylcyclopentene, cyclopentadiene,cyclooctadiene, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, 5-methylidene-2-norbornene, vinylcyclohexene,vinylcyclopentene, vinylcyclobutene, vinylcyclooctene,5-vinyl-2-norbornene, 7,7-dimethyl-bicyclo[2.2.1]hept-2-ene,tricyclo[4.2.1.0^(2,5)]nona-3,7-diene,5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene,methyl-bicyclo[2.2.1]hept-2-ene,2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene,5-ethenylidene-bicyclo[2.2.1]hept-2-ene,5,6-dimethyl-bicyclo[2.2.1]hept-2-ene,5-ethynyl-bicyclo[2.2.1]hept-2-ene, 7-oxanorbornene, 7-oxanorbornadiene,and substituted derivatives thereof, and preferably norbornene,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, vinylcyclohexene, and 5-vinyl-2-norbornene,most preferably 5-ethylidene-2-norbornene.

In some embodiments, the cyclic olefin monomer is preferably a cyclicdiene monomer such as cyclopentadiene, cyclooctadiene, norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, vinylcyclohexene, vinylcyclopentene,vinylcyclobutene, vinylcyclooctene, 5-vinyl-2-norbornene,tricyclo[4.2.1.0^(2,5)]nona-3,7-diene, preferably norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene, and5-methylidene-2-norbornene, most preferably 5-ethylidene-2-norbornene.

Generally, the process of this invention produces olefin polymers,preferably ethylene-C₃ to C₁₂ alpha olefin-cyclic diene copolymers. In apreferred embodiment, the polymers produced herein are copolymers ofethylene preferably having from: 1) 1 to 90 mole % (alternately from 1to 80 mole %, alternately from 1 to 60 mole %, alternately from 5 to to50 mole %, alternately from 10 to 45 mole %, alternately from 20 to 40mole %) of one or more C₃ to C₁₂ olefin comonomer (preferably C₃ to C₁₂alpha-olefin, preferably propylene, butene, hexene, octene, decene,dodecene, preferably propylene, butene, hexene, octene, most preferablypropylene); 2) from 0 to 25 mole % (alternately from 0.5 to 20 mole %,alternately from 1 to 15 mole %, alternately from 3 to 12 mole %,preferably from 3 to 10 mole %) of one or more of cyclic dienecomonomers (preferably norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, and or 5-vinyl-2-norbornene, most preferably5-ethylidene-2-norbornene); and 3) the balance preferably made up of byethylene.

In a preferred embodiment, the monomer is ethylene preferably havingfrom 1 to 90 mole % (alternately from 1 to 80 mole %, alternately from 1to 60 mole %, alternately from 5 to 50 mole %, alternately from 10 to 45mole %, alternately from 20 to 40 mole %) and the comonomer ispropylene, preferably from 1 to 60 mole % propylene, alternately 5 to 55mole %, alternatively 10 to 45 mole %, alternatively 20 to 40 mol %, andthe cyclic olefin monomer is a cyclic diene, preferably from 1 to 40 mol%, alternatively from 1 to 25 mole %, alternately 1 to 20 mole %,alternatively 1 to 10 mole %, alternatively 1 to 5 mole %, alternatively1 to 3 mole % of one or more of norbornadiene,5-ethylidene-2-norbornene, dicyclopentadiene, and/or5-vinyl-2-norbornene, most preferably 5-ethylidene-2-norbornene.

In a preferred embodiment, the monomer is ethylene preferably present atfrom 20 to 70 mole % (alternately from 30 to 60 mole %, alternately from35 to 55 mole %, alternately from 40 to 50 mole %, the comonomer ispropylene, preferably present at from 30 to 70 mole % propylene,alternately 40 to 60 mole %, alternatively 45 to 55 mole %,alternatively 50 to 60 mol %, and the cyclic olefin monomer is a cyclicdiene, preferably present at from 1 to 20 mol %, alternatively from 1 to15 mole %, alternately 1 to 10 mole %, alternatively 1 to 5 mole %,alternatively 1 to 3 mole %, alternatively 1 to 2 mole % of one or moreof norbornadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, and/or5-vinyl-2-norbornene, most preferably 5-ethylidene-2-norbornene.

In a preferred embodiment, the ethylene-propylene-cyclic monomercopolymer contains greater than 50% vinyl end-group unsaturation,alternately greater than 60% vinyl end-group unsaturation, alternatelygreater than 70% vinyl end-group unsaturation, alternately alternatelygreater than 80% vinyl end-group unsaturation, alternately greater than90% vinyl end-group unsaturation, alternately greater than 95% vinylend-group unsaturation.

Typically, the polymers produced herein have an Mw of 3,000 to 5,000,000g/mol (alternatively 5,000 to 3,000,000 g/mol, alternatively 10,000 to2,500,000 g/mol, alternatively 50,000 to 2,00,000 g/mol, alternatively75,000 to 1,000,000 g/mol, alternatively 100,000 to 500,000 g/mol,alternatively 100,000 to 250,000 g/mol), and/or an Mw/Mn of greater than1 to 40 (alternately 1.2 to 20, alternately 1.3 to 10, alternately 1.4to 5, 1.5 to 4, alternately 1.5 to 3).

In a preferred embodiment the polymer produced herein has a unimodal ormultimodal molecular weight distribution (MWD=Mw/Mn) as determined byGel Permeation Chromatography (GPC). By “unimodal” is meant that the GPCtrace has one peak or inflection point. By “multimodal” is meant thatthe GPC trace has at least two peaks or inflection points. An inflectionpoint is that point where the second derivative of the curve changes insign (e.g., from negative to positive or vice versus).

In a preferred embodiment the copolymers produced herein have acomposition distribution breadth index (CDBI) of 50% or more, preferably60% or more, preferably 70% or more. CDBI is a measure of thecomposition distribution of monomer within the polymer chains and ismeasured by the procedure described in WO 93/03093, published Feb. 18,1993, specifically columns 7 and 8 as well as in Wild et al, J. Poly.Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Pat. No.5,008,204, including that fractions having a weight average molecularweight (Mw) below 10,000 g/mol are ignored when determining CDBI.

The polymers produced herein typically have at least 50% allyl chainends or 3-alkyl chain ends (preferably at least 60%, at least 70%, atleast 80%, at least 90%, at least 95%, at least 98%, or at least 99%allyl chain ends and/or 3-alkyl chain ends).

An allyl chain end is represented by CH₂CH—CH₂—, as shown in theformula:

where M represents the polymer chain. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” and “vinyl terminated” are used interchangeably in the followingdescription. The number of allyl chain ends, vinylidene chain ends,vinylene chain ends, and other unsaturated chain ends is determinedusing ¹H NMR at 120° C. using deuterated tetrachloroethane as thesolvent on an at least 250 MHz NMR spectrometer, and in selected cases,confirmed by ¹³C NMR. Resconi has reported proton and carbon assignments(neat perdeuterated tetrachloroethane used for proton spectra, while a50:50 mixture of normal and perdeuterated tetrachloroethane was used forcarbon spectra; all spectra were recorded at 100° C. on a BRUKERspectrometer operating at 500 MHz for proton and 125 MHz for carbon) forvinyl terminated oligomers in J. American Chemical Soc., 114, 1992, pp.1025-1032 that are useful herein. Allyl chain ends are reported as amolar percentage of the total number of moles of unsaturated groups(that is, the sum of allyl chain ends, vinylidene chain ends, vinylenechain ends, and the like).

A 3-alkyl chain end (where the alkyl is a C₁ to C₃₈ alkyl), alsoreferred to as a “3-alkyl vinyl end group” or a “3-alkyl vinyltermination”, is represented by the formula:

where “****” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, or a C₁ to C₂₀ alkyl group, such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, andthe like. The amount of 3-alkyl chain ends is determined using ¹H NMR asset out below. The chemical shift regions for the olefin types aredefined to be between the following spectral regions.

Region Number of hydrogens Unsaturation Type (ppm) per structure Vinyl4.98-5.13 2 Vinylidene (VYD) 4.69-4.88 2 Vinylene 5.31-5.55 2Trisubstituted 5.11-5.30 1

In a preferred embodiment of the invention, the polymer produced hereinis an ethylene-propylene-cyclic monomer copolymer having from 0.1 to 50mol % comonomer) and having: 1) at least 50% allyl chain ends; and 2) anMw of 5000 g/mol or more.

In a preferred embodiment of the invention, the polymer produced hereinis a has a branching index (g′_(vis)) of 0.95 or less, preferably 0.90or less, preferably 0.87 or less, preferably 0.85 or less, preferably0.80 or less, preferably 0.75 or less, as determined by GPC, asdescribed in the Examples section below.

The polymers prepared herein may be functionalized by reacting aheteroatom containing group with the polymer with or without a catalyst.Examples include catalytic hydrosilylation, ozonolysis,hydroformylation, or hydroamination, sulfonation, halogenation,hydrohalogenation, hydroboration, epoxidation, or Diels-Alder reactionswith polar dienes, Friedel-Crafts reactions with polar aromatics,maleation with activators such as free radical generators (e.g.,peroxides). The functionalized polymers can be used in oil additives, asanti-fogging or wetting additives, adhesion promoters and many otherapplications. Preferred uses include additives for lubricants and orfuels. Preferred heteroatom containing groups include, amines,aldehydes, alcohols, acids, anhydrides, sulphonates, particularlysuccinic acid, maleic acid and maleic anhydride.

Other uses of the functionalized polymers include as plasticizers,surfactants for soaps, detergents, fabric softeners, antistatics, etc.Preferred heteroatom containing groups include, amines, aldehydes,alcohols, acids, anhydrides, and sulphonates, particularly succinicacid, maleic acid and maleic anhydride.

In some embodiments the polymers produced herein are functionalized asdescribed in U.S. Pat. No. 6,022,929; A. Toyota, T. Tsutsui, and N.Kashiwa, Polymer Bulletin 48, 213-219, 2002; and J. Am. Chem. Soc.,1990, 112, 7433-7434.

Blends

In another embodiment, the polymer produced herein is combined with oneor more additional polymers prior to being formed into a film, moldedpart or other article. Other useful polymers include polyethylene,isotactic polypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In a preferred embodiment, the polymer is present in the above blends,at from 10 to 99 wt %, based upon the weight of the polymers in theblend, preferably 20 to 95 wt %, even more preferably at least 30 to 90wt %, even more preferably at least 40 to 90 wt %, even more preferablyat least 50 to 90 wt %, even more preferably at least 60 to 90 wt %,even more preferably at least 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

Any of the foregoing polymers, including blends thereof, may be used ina variety of end-use applications. Such applications include, forexample, mono- or multi-layer blown, extruded, and/or shrink films.These films may be formed by any number of well known extrusion orcoextrusion techniques, such as a blown bubble film processingtechnique, wherein the composition can be extruded in a molten statethrough an annular die and then expanded to form a uni-axial or biaxialorientation melt prior to being cooled to form a tubular, blown film,which can then be axially slit and unfolded to form a flat film. Filmsmay be subsequently unoriented, uniaxially oriented, or biaxiallyoriented to the same or different extents. One or more of the layers ofthe film may be oriented in the transverse and/or longitudinaldirections to the same or different extents. The uniaxially orientationcan be accomplished using typical cold drawing or hot drawing methods.Biaxial orientation can be accomplished using tenter frame equipment ora double bubble process and may occur before or after the individuallayers are brought together. Typically the films are oriented in theMachine Direction (MD) at a ratio of up to 15, preferably between 5 and7, and in the Transverse Direction (TD) at a ratio of up to 15,preferably 7 to 9. However, in another embodiment the film is orientedto the same extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In a preferred embodiment, one or both of thesurface layers is modified by corona treatment.

Molded Products

The polymers described herein (preferably ethylene-propylene-cyclicmonomer polymers) and blends thereof may also be used to prepare moldedproducts in any molding process, including but not limited to, injectionmolding, gas-assisted injection molding, extrusion blow molding,injection blow molding, injection stretch blow molding, compressionmolding, rotational molding, foam molding, thermoforming, sheetextrusion, and profile extrusion. The molding processes are well knownto those of ordinary skill in the art.

Further, the polymers described herein (preferablyethylene-propylene-cyclic monomer polymers) may be shaped into desirableend use articles by any suitable means known in the art. Thermoforming,vacuum forming, blow molding, rotational molding, slush molding,transfer molding, wet lay-up or contact molding, cast molding, coldforming matched-die molding, injection molding, spray techniques,profile co-extrusion, or combinations thereof are typically usedmethods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Typically, an extrudate film of the composition ofthis invention (and any other layers or materials) is placed on ashuttle rack to hold it during heating. The shuttle rack indexes intothe oven which pre-heats the film before forming. Once the film isheated, the shuttle rack indexes back to the forming tool. The film isthen vacuumed onto the forming tool to hold it in place and the formingtool is closed. The tool stays closed to cool the film and the tool isthen opened. The shaped laminate is then removed from the tool. Thethermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution.

Blow molding is another suitable forming means for use with thecompositions of this invention, which includes injection blow molding,multi-layer blow molding, extrusion blow molding, and stretch blowmolding, and is especially suitable for substantially closed or hollowobjects, such as, for example, gas tanks and other fluid containers.Blow molding is described in more detail in, for example, CONCISEENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, pp. 90-92 (JacquelineI. Kroschwitz, ed., John Wiley & Sons 1990).

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheets may be made either byextruding a substantially flat profile from a die, onto a chill roll, oralternatively by calendaring. Sheets are generally considered to have athickness of from 10 mils to 100 mils (254 μm to 2540 μm), although anygiven sheet may be substantially thicker.

Any of the foregoing polymers, including compounds thereof, may be usedin a variety of end-use applications. Such applications include, forexample, mono- or multi-layer blown, extruded, and/or shrink films.These films may be formed by any number of well known extrusion orcoextrusion techniques, such as a blown bubble film processingtechnique, wherein the composition can be extruded in a molten statethrough an annular die and then expanded to form a uni-axial or biaxialorientation melt prior to being cooled to form a tubular, blown film,which can then be axially slit and unfolded to form a flat film.

The present polymer compositions can further be used in a variety ofapplications such as barrier layers, weather seals, coolant hoses,roofing membranes, wire and cable insulation, dynamically vulcanizedalloys, power transmission belts, engine mounts, thermoplastic blends,elastic fibers, and the like.

The present polymer compositions can further be used in automotiveparts, consumer goods, industrial goods, construction materials, andpackaging materials, including, but are not limited to, an extrudedarticle, such as an automotive weatherseal, a non-automotiveweatherseal, a building profile; a molded article, such as a seal, agasket; a hose, such as air hose, heat hose, garden hose, industry hose;a roof sheet; a film; or a cable jacket.

Experimental Test Methods for Large Scale Polymerizations Gel PermeationChromatography

Mw, Mn, Mz, number of carbon atoms and g′_(vis) are determined by usinga High Temperature Size Exclusion Chromatograph (either from WatersCorporation or Polymer Laboratories), equipped with three in-linedetectors, a differential refractive index detector (DRI), a lightscattering (LS) detector, and a viscometer. Experimental details,including detector calibration, are described in: T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B LS columns are used. The nominal flow rate is 0.5cm³/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 145° C. Solvent for theexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SizeExclusion Chromatograph. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 145° C. The injectionconcentration is from 0.75 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector are purged. Flow rate in the apparatusis then increased to 0.5 ml/minute, and the DRI is allowed to stabilizefor 8 to 9 hours before injecting the first sample. The LS laser isturned on 1 to 1.5 hours before running the samples. The concentration,c, at each point in the chromatogram is calculated from thebaseline-subtracted DRI signal, I_(DRI), using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and 2=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers,0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second viral coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(θ) is the form factor for amonodisperse random coil, and K_(o) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}( {{dn}/{dc}} )}^{2}}{\lambda^{4}N_{A}}$

where NA is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits. The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. My is the viscosity-average molecular weight based onmolecular weights determined by LS analysis.

Mooney Large viscosity (ML) and Mooney Relaxation Area (MLRA): ML andMLRA are measured using a Mooney viscometer according to ASTM D-1646,modified as detailed in the following description. A square sample isplaced on either side of the rotor. The cavity is filled bypneumatically lowering the upper platen. The upper and lower platens areelectrically heated and controlled at 125° C. The torque to turn therotor at 2 rpm is measured by a torque transducer. Mooney viscometer isoperated at an average shear rate of 2 s⁻¹. The sample is pre-heated for1 minute after the platens are closed. The motor is then started and thetorque is recorded for a period of 4 minutes. The results are reportedas ML (1+4) 125° C., where M is the Mooney viscosity number, L denoteslarge rotor, 1 is the pre-heat time in minutes, 4 is the sample run timein minutes after the motor starts, and 125° C. is the test temperature.

The torque limit of the Mooney viscometer is about 100 Mooney units.Mooney viscosity values greater than about 100 Mooney unit cannotgenerally be measured under these conditions. In this event, anon-standard rotor design is employed with a change in Mooney scale thatallows the same instrumentation on the Mooney viscometer to be used formore viscous polymers. This rotor that is both smaller in diameter andthinner than the standard Mooney Large (ML) rotor is termed MST—MooneySmall Thin. Typically when the MST rotor is employed, the test is alsorun at different time and temperature. The pre-heat time is changed fromthe standard 1 minute to 5 minutes and the test is run at 200° C.instead of the standard 125° C. Thus, the value will be reported as MST(5+4), 200° C. Note that the run time of 4 minutes at the end which theMooney reading is taken remains the same as the standard conditions.According to EP 1 519 967, one MST point is approximately 5 ML pointswhen MST is measured at (5+4@200° C.) and ML is measured at (1+4@125°C.). The MST rotor should be prepared as follows:

-   -   1. The rotor should have a diameter of 30.48+/−0.03 mm and a        thickness of 2.8+/−0.03 mm (tops of serrations) and a shaft of        11 mm or less in diameter.    -   2. The rotor should have a serrated face and edge, with square        grooves of 0.8 mm width and depth of 0.25-0.38 mm cut on 1.6 mm        centers. The serrations will consist of two sets of grooves at        right angles to each other (form a square crosshatch).    -   3. The rotor shall be positioned in the center of the die cavity        such that the centerline of the rotor disk coincides with the        centerline of the die cavity to within a tolerance of        +/−0.25 mm. A spacer or a shim may be used to raise the shaft to        the midpoint.    -   4. The wear point (cone shaped protuberance located at the        center of the top face of the rotor) shall be machined off flat        with the face of the rotor.

The MLRA data is obtained from the Mooney viscosity measurement when therubber relaxes after the rotor is stopped. The MLRA is the integratedarea under the Mooney torque-relaxation time curve from 1 to 100seconds. The MLRA is a measure of chain relaxation in molten polymer andcan be regarded as a stored energy term which suggests that, after theremoval of an applied strain, the longer or branched polymer chains canstore more energy and require longer time to relax. Therefore, the MLRAvalue of a bimodal rubber (the presence of a discrete polymeric fractionwith very high molecular weight and distinct composition) or a longchain branched rubber are larger than a broad or a narrow molecularweight rubber when compared at the same Mooney viscosity values.

Mooney Relaxation Area is dependent on the Mooney viscosity of thepolymer, and increases with increasing Mooney viscosity. In order toremove the dependence on polymer Mooney Viscosity, a corrected MLRA(cMLRA) parameter is used, where the MLRA of the polymer is normalizedto a reference of 80 Mooney viscosity. The formula for cMLRA is providedbelow:

${cMRLA} = {{MRLA}( \frac{80}{ML} )}^{1.4\; 4}$

where MLRA and ML are the Mooney Relaxation Area and Mooney viscosity ofthe polymer sample measured at 125° C.

Alternatively, the ratio MLRA/ML may be used to remove the dependence onpolymer Mooney Viscosity. This ratio has the dimension of time. A higherMLRA/ML number signifies a higher degree of melt elasticity. Long chainbranching will slow down the relaxation of the polymer chain, henceincreasing the value of MLRA/ML.

Ethylene content is determined using FTIR according the ASTM D3900 andis not corrected for diene content. ENB content is determined using FTIRaccording to ASTM D6047.

Examples Starting Materials

All manipulations with air and moisture sensitive compounds wereperformed either in an atmosphere of thoroughly purified argon usingstandard Schlenk techniques or in a controlled atmosphere glove box(Vacuum Atmospheres Co.). Tetrahydrofuran (THF, Merck=Merck KGaA,Darmstadt, Germany) and diethyl ether (ether, Merck) for synthesis werepurified by distillation over LiA1H₄, and stored over sodiumbenzophenone ketyl under an inert atmosphere; prior to use, the solventswere distilled from the benzophenone ketyl. Hydrocarbon solvents such astoluene (Merck), and hexanes (Merck) were typically distilled over CaH₂,and were stored over Na/K alloy under an inert atmosphere; prior to use,the solvents were distilled from the Na/K alloy. Methylene chloride (andCCl₂D₂ for NMR measurements) was distilled and stored over CaH₂ under aninert atmosphere; prior to use, the solvent was distilled from the CaH₂.Celite (Aldrich) was dried in a vacuum oven at 180° C. p-Toluenesulfonicacid (TsOH, Aldrich), 2.5 M ^(n)BuLi in hexanes (Chemetall GmbH), MeMgBrin ether (Aldrich), and HfCl₄ (Strem), Na₂SO₄ (Akzo Nobel), methanol(Merck), sodium lump (Merck), ZnCl₂ (Merck), 3-chloropropanoyl chloride(Acros), potassium hydroxide (Merck), AlCl₃ (Merck), 12 M HCl (dilutedas needed; Reachim, Moscow, Russia), 96% H₂SO₄ (diluted as needed;Reachim), anhydrous K₂CO₃ (Merck), CuCN (Merck), hydrazine hydrate(Merck), silica gel 60 (40-63 um; Merck), NaHCO₃ (Merck), ethyleneglycol (Merck), Na₂CO₃ (Aldrich), and CDCl₃ (Deutero GmbH) were used asreceived.

1,1-Dichlorosilolane was obtained as described in [West, R. J. Am. Chem.Soc., 1954, 76, 6015-6017] and [Denmark, S. E.; Griedel, B. D.; Coe, D.M.; Schnute, M. E., J. Am. Chem. Soc., 1994, 116, 7026-7043].

Analytical and semi-preparative liquid chromatography was performedusing a Waters Delta 600 HPLC system including a 996 Photodiode ArrayDetector, Nova-Pack C18 or HR Silica (60A, 6 μm, 3.9 and 19×300 mm) andSymmetry C18 (5 μm, 4.6×250 mm) columns. MPLC (Medium Pressure LiquidChromatography, pressure 5-15 bars) was performed using MPLC glasscolumns and fittings (Ace Glass), a PD5130 pump drive equipped with a J1gear-well pump head (Heidolph), a 996 Photodiode Array Detector and aFraction Collector II (Waters Corp.). ¹H and ¹³C spectra were recordedwith a Brucker Avance-400 spectrometer. Chemical shifts for ¹H and ¹³Cwere measured relative to tetramethylsilane (TMS). ¹H NMR spectralassignments were made on the basis of double resonance and NuclearOverhauser Effect (NOE) experiments. CHN microanalyses were done using aCHN-O-Rapid analyzer (Heraecus Ltd., Banau, Germany).

Synthesis ofrac-cyclotetramethylenesilylene-bis[4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl]hafniumdimethyl (compound 19) 4,7-Dimethylindane

A mixture of 124 g (2.21 mol) of KOH, 91.4 g (570.5 mmol) of4,7-dimethylindan-1-one, 102 ml of hydrazine hydrate, and 1100 ml ofethylene glycol was heated under reflux for 5 h. Then, the refluxcondenser was replaced by a Claisen distillation head with condenser,and a mixture of water, NH₂NH₂, the product and ethylene glycol wasdistilled until the vapor temperature reached 195° C. The obtaineddistillate was diluted with 1000 ml of water, and crude product wasextracted with 3×250 ml of dichloromethane. The combined organic extractwas washed by 1 M HCl, dried over anhydrous K₂CO₃, and then passedthrough a short pad of silica gel 60 (40-63 um). The obtained filtratewas evaporated to dryness to give a slightly yellowish liquid. Thisliquid was distilled in vacuum to give 68.1 g (82%) of4,7-dimethylindane as a colorless liquid, b.p. 88-90° C./10 mm Hg.

Anal. calc. for C₁₁H₁₄: C, 90.35; H, 9.65. Found: C, 90.31; H, 9.48. ¹HNMR (CDCl₃): δ 6.86 (s, 2H), 2.82 (t, J=7.6 Hz, 4H), 2.21 (s, 6H), 2.05(quint, J=7.6 Hz, 2H). ¹³C{¹H} NMR (CDCl₃): δ 142.53, 130.84, 126.99,31.62, 24.17, 18.86.

4,8-Dimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one

To a stirred suspension of 133.4 g (1.0 mol) of AlCl₃ in 600 ml ofdichloromethane a solution of 111.5 g (878 mmol) of 3-chloropropanoylchloride and 121.8 g (833 mmol) of 4,7-dimethylindane in 100 ml ofdichloromethane was added dropwise over 3 h at room temperature. Thismixture was stirred additionally overnight at room temperature and thenpoured on 1000 g of crushed ice. The organic layer was separated, andthe aqueous layer was extracted with 3×100 ml of dichloromethane. Thecombined organic extract was washed by aqueous K₂CO₃, dried over K₂CO₃,passed through a short pad of silica gel 60 (40-63 um), and thenevaporated to dryness to give dark oily liquid. This liquid was added to1000 ml of sulfuric acid and then stirred for 1 h at room temperature.The resulting dark solution was heated for 30 min to 90° C. and thenstirred for one hour at the same temperature. After cooling to roomtemperature the reaction mixture was poured on 2000 g of crushed ice and3000 ml of cold water. Then, 1 liter of dichloromethane was added. Theorganic layer was separated, and the aqueous layer was extracted withdichloromethane (100 ml per 900 ml of aqueous phase). The combinedorganic extract was washed by water, then by aqueous K₂CO₃, dried overK₂CO₃ and passed through a short layer of silica gel 60 (40-63 um). Theelute was evaporated to ca. 500 ml, and the title product was isolatedby flash-chromatography on 1000 ml of silica gel 60 (40-63 um; eluent:dichloromethane). This procedure gave 90.3 g (54%) of4,8-dimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one as a slightlyyellowish solid.

Anal. calc. for C₁₄H₁₆O: C, 83.96; H, 8.05. Found: C, 84.30; H, 8.27. ¹HNMR (CDCl₃): δ 2.94-2.82 (m, 6H), 2.70-2.62 (m, 2H), 2.53 (s, 3H), 2.19(s, 3H), 2.12 (quin, J=7.5 Hz, 2H). ¹³C{¹H} NMR (CDCl₃): δ 208.15,153.92, 149.93, 143.01, 132.88, 131.04, 127.84, 37.40, 31.98, 30.72,24.57, 23.70, 14.33, 14.30.

4,8-Dimethyl-1,2,3,5-tetrahydro-s-indacene

To a solution of 90.3 g (450.7 mmol) of4,8-dimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one in 900 ml of THFcooled to 5° C. 25.6 g (677 mmol) of NaBH₄ was added. Further on, 250 mlof methanol was added dropwise to this mixture by vigorous stirring forca. 5 h at 5° C. The resulting mixture was evaporated to dryness, andthe residue was partitioned between 1000 ml of dichloromethane and 700ml of 1 M HCl. The organic layer was separated, the aqueous layer wasadditionally extracted with 200 ml of dichloromethane. The combinedorganic extract was evaporated to dryness to give a white solid. To asolution of this solid in 1500 ml of toluene 0.5 g of TsOH was added,this mixture was refluxed with Dean-Stark head for 15 min and thencooled to room temperature using water bath. The resulting solution waswashed by 10% aqueous Na₂CO₃, the organic layer was separated, theaqueous layer was extracted with 2×150 ml of dichloromethane. Thecombined organic extract was dried over K₂CO₃ and then passed through ashort layer of silica gel 60 (40-63 um). The silica gel layer wasadditionally washed by 100 ml of dichloromethane. The combined organicelute was evaporated to dryness to give a brownish solid mass. Theproduct was isolated by flash-chromatography on 1000 ml of silica gel 60(40-63 um; eluent: hot hexane) followed by recrystallization fromn-hexane. This procedure gave 65.4 g (79%) of4,8-dimethyl-1,2,3,5-tetrahydro-s-indacene as a white crystalline solid.

Anal. calc. for C₁₄H₁₆: C, 91.25; H, 8.75. Found: C, 91.11; H, 8.62. ¹HNMR (CDCl₃): δ 6.97 (dt, J=5.5 Hz, J=1.9 Hz, 1H), 6.48 (dt, J=5.5 Hz,J=1.9 Hz, 1H), 3.27 (s, 2H), 2.93-2.85 (m, 4H), 2.33 (s, 3H), 2.25 (s,3H), 2.11 (quin, J=7.5 Hz, 2H). ¹³C{¹H} NMR (CDCl₃): δ 141.97, 141.27,140.91, 139.73, 132.40, 130.48, 126.11, 123.36, 37.93, 31.54, 31.46,25.00, 15.66, 15.42.

rac-cyclotetramethylenesilylene-bis[4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl]hafnium dichloride, otherwisenamedrac-1,1-Silolanediyl-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafniumdichloride

To a solution of 13.8 g (75 mmol) of4,8-dimethyl-1,2,3,5-tetrahydro-s-indacene in 420 ml of ether 30 ml (75mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion at −50° C.This mixture was stirred for 3 h at room temperature, then the resultinglight-yellow solution with a large amount of heavy white precipitate wascooled to −50° C., and 200 mg of CuCN was added. The resulting mixturewas stirred for 15 min at −25° C., and then 5.82 g (37.52 mmol) of1,1-dichlorosilolane was added in one portion. The formed mixture wasstirred overnight at ambient temperature, then it was filtered throughglass frit (G4), and the obtained slightly yellowish solution wasfurther used without an additional purification. To the above-preparedsolution of 37.5 mmol (assuming almost quantitative yield) of1,1-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)silolane cooledto −50° C. 30.0 ml (75 mmol) of 2.5 M ^(n)BuLi in hexanes was added inone portion. This mixture was stirred overnight at room temperature. Theresulting almost colorless solution with a lot of white precipitate wascooled to −50° C., and 12.0 g (37.5 mmol) of HfCl₄ was added. Thereaction mixture was stirred for 24 h resulting in light red solutionwith a large amount of yellow precipitate. The obtained mixture wasevaporated to dryness, and the residue was heated with 250 ml oftoluene. This suspension was filtered while hot through glass frit (G4).The filtrate was evaporated to 120 ml and then heated to dissolve theformed precipitate. Yellow powder precipitated overnight at roomtemperature was collected and dried in vacuum. This procedure gave 8.10g of purerac-1,1-silolanediyl-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafniumdichloride. The mother liquor was evaporated to ca. 60 ml. Yellow powderprecipitated from this solution overnight at room temperature wascollected and dried in vacuum. This procedure gave 3.10 g ofrac-1,1-silolanediyl-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafniumdichloride. Again, the mother liquor was evaporated to ca. 25 ml, and 60ml of n-hexane was added. After stirring for 30 min the precipitatedorange solid was filtered off and then dried in vacuum. This proceduregave 5.00 g of a ca. 3:1 mixture of rac-/meso-complexes. Thus, the totalyield of rac- and meso-complexes isolated in this synthesis was 16.2 g(62%).

Anal. calc. for C₃₂H₃₆Cl₂HfSi: C, 55.05; H, 5.20. Found: C, 55.24; H,5.39. ¹H NMR (CDCl₃): δ 6.84 (d, J=3.5 Hz, 2H), 6.00 (d, J=3.5 Hz, 2H),3.07-2.79 (m, 8H), 2.44 (s, 6H), 2.25 (s, 6H), 2.23-2.15 (m, 2H),2.12-1.93 (m, 4H), 1.92-1.73 (m, 4H), 1.67-1.57 (m, 2H). ¹³C{¹H} NMR(CDCl₃): δ 143.56, 142.42, 131.44, 127.03, 125.65, 124.73, 117.02,117.01, 89.60, 31.80, 31.01, 26.78, 25.17, 19.50, 17.44, 15.78.

rac-cyclotetramethylenesilylene-bis[4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl]hafnium dimethyl, otherwisenamedrac-1,1-Silolanediyl-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafniumdimethyl (Compound 19)

To a solution of 8.10 g (11.6 mmol) ofrac-1,1-silolanediyl-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafniumdichloride in a mixture of 140 ml of toluene and 40 ml of ether 24.0 ml(50.6 mmol) of 2.11 M MeMgBr in ether was added. The resulting mixturewas refluxed for 30 min, then evaporated to ca. 50 ml, heated andfiltered while hot through glass frit (G3) to remove insoluble magnesiumsalts. The filter cake was additionally washed with 2×15 ml of toluene.The combined filtrate was evaporated to ca. 400 ml, heated and againfiltered while hot through glass frit (G3). Light yellow crystalsprecipitated from the filtrate overnight at room temperature werecollected and dried in vacuum. This procedure gave 5.60 g (74%) of purerac-1,1-silolanediyl-bis(4,8-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafniumdimethyl.

Anal. calc. for C₃₄H₄₂HfSi: C, 62.13; H, 6.44. Found: C, 62.19; H, 6.60.¹H NMR (CDCl₃): δ 6.83 (d, J=3.4 Hz, 2H), 5.75 (d, J=3.4 Hz, 2H),3.01-2.88 (m, 4H), 2.88-2.73 (m, 4H), 2.35 (s, 6H), 2.29 (s, 6H),2.18-2.07 (m, 2H), 2.02 (quin, J=7.4 Hz, 4H), 1.81-1.67 (m, 2H),1.67-1.54 (m, 2H), 1.53-1.44 (m, 2H), −1.79 (s, 6H). ¹³C{¹H} NMR(CDCl₃): δ 140.87, 139.99, 129.14, 126.21, 125.30, 124.97, 117.81,110.49, 84.94, 38.73, 31.74, 30.99, 26.86, 25.40, 19.38, 17.47, 16.03.

List of Catalysts

Compounds used in the following polymerization examples include thefollowing wherein the associated number is the compound number, alsoreferred to the CAT ID in polymerization example tables.

rac-cyclopentamethylenesilylene-bis [4,7-dimethylinden-1-yl]hafniumdimethyl (12)  

rac-cyclotetramethylenesilyene-bis [4,7-dimethylinden-1-yl]hafniumdimethyl (14)  

rac-cyclotetramethylenesilyene-bis[4,8-dimethyl-1,2,3-trihydro-s-indacen-5- yl]hafnium dimethyl (19)  

rac-cyclotetramethylenesilyene-bis (2,4,7-trimethylinden-1-yl)hafniumdimethyl (2)  

rac-cyclotetramethylenesilylene-bis[4,6,8-trimethyl-1,2,3-trihydro-s-indacen-5- yl]hafnium dimethyl (16)  

rac-cyclotetramethylenesilylene- bis(2-methyl-4-isopropylinden-1-yl)hafnium dichloride(8)  

rac-cyclotrimethylenesilylene-bis (2,4,7-trimethylinden-1-yl)hafniumdichloride (17)  

rac-cyclotetramethylenesilylene-bis (2-ethyl-4-cyclopropylinden-1-yl)hafnium dichloride (5)  

rac-cyclotrimethylenesilylene-bis(2- ethyl-4-cyclopropylinden-1-yl)hafnium dichloride (6)  

rac-dimethlenesilylene-bis(2-methyl- 4-phenylinden-1-yl)zirconiumdimethyl (20)  

Compounds 2, 5, 6, 8, 12, 14, 16, and 17 were prepared as described inU.S. Ser. No. 14/325,449, filed Jul. 8, 2014 and U.S. Ser. No.61/847,442, filed Jul. 17, 2013.

Comparative compounds used in the following polymerization examplesinclude compounds 2, 5, 6, 8, 16, 17 and 20 all of which have 2 alkylsubstituents on the indenyl rings.

Small Scale Polymerization Examples

Solutions of the pre-catalysts (Compounds 2, 5, 6, 8, 12, 14, 16, 17,19, and 20) were made using toluene (ExxonMobil Chemical-anhydrous,stored under N₂) (98%). Pre-catalyst solutions were typically 0.5mmol/L. When noted, some pre-catalysts were pre-alkylated usingtriisobutyl aluminum (TiBAl, neat, AkzoNobel); prealkylation wasperformed by first dissolving the pre-catalyst in the appropriate amountof toluene, and then adding 20 equivalents of TiBAl such that the finalpre-catalyst solution was 0.5 mmol precatalyst/L and 10 mmol TiBAl/L.

Solvents, polymerization grade toluene and/or isohexanes were suppliedby ExxonMobil Chemical Co. and are purified by passing through a seriesof columns: two 500 cc Oxyclear cylinders in series from Labclear(Oakland, Calif.), followed by two 500 cc columns in series packed withdried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500cc columns in series packed with dried 5 Å mole sieves (8-12 mesh;Aldrich Chemical Company).

5-ethylidene2-norbornene (ENB, Aldrich) was sparged by nitrogen,filtered through basic alumina (Aldrich Chemical Company, BrockmanBasic 1) and stored under an inert atmosphere of dry nitrogen.

Polymerization grade ethylene was used and further purified by passingit through a series of columns: 500 cc Oxyclear cylinder from Labclear(Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å molesieves (8-12 mesh; Aldrich Chemical Company), and a 500 cc column packedwith dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company).

Activation of the pre-catalysts was by dimethylaniliniumtetrakisperfluorophenylborate (Boulder Scientific and Albemarle Corp).Dimethylanilinium tetrakisperfluorophenylborate was typically used as a5 mmol/L solution in toluene.

For polymerization runs using dimethylaniliniumtetrakisperfluorophenylborate tri-n-octylaluminum (TnOAl, Neat,AkzoNobel) was also used as a scavenger prior to introduction of theactivator and pre-catalyst into the reactor. TnOAl was typically used asa 5 mmol/L solution in toluene.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N₂) drybox usingautoclaves equipped with an external heater for temperature control,glass inserts (internal volume of reactor=23.5 mL), septum inlets,regulated supply of nitrogen, ethylene and propylene, and equipped withdisposable PEEK mechanical stirrers (800 RPM). The autoclaves wereprepared by purging with dry nitrogen at 110° C. or 115° C. for 5 hoursand then at 25° C. for 5 hours.

Ethylene/ENB Copolymerization:

The reactor was prepared as described above, and then purged withethylene. For dimethylanilinium tetrakisperfluorophenylborate activatedruns, isohexane, ENB (50 μL) and scavenger (TnOAl, 0.075 mol) were addedvia syringe at room temperature and atmospheric pressure. The reactorwas then brought to process temperature (100° C.) and charged withethylene to process pressure (100 psig=790.8 kPa) while stirring at 800RPM. The activator solution (0.088 umol of activator), followed by thepre-catalyst solution (0.080 umol of pre-catalyst), was injected viasyringe to the reactor at process conditions. Ethylene was allowed toenter (through the use of computer controlled solenoid valves) theautoclaves during polymerization to maintain reactor gauge pressure(+/−2 psig). Reactor temperature was monitored and typically maintainedwithin +/−1° C. Polymerizations were halted by addition of approximately50 psi CO₂/Ar (50/50) gas mixture to the autoclave for approximately 30seconds. The polymerizations were quenched after a predeterminedcumulative amount of ethylene had been added (maximum quench value of 20psi) or for a maximum of 30 minutes polymerization time (maximum quenchtime). Afterwards, the reactors were cooled and vented. While stillunder an inert atmosphere, the polymers were stabilized with theaddition of a 50 uL solution of a Irganox 1076 and Irgafos 168 intoluene (prepared by dissolving 0.5 g of each antioxidant in a total of10 ml toluene). Polymers were isolated after the solvent was removedin-vacuo. Yields reported include total weight of polymer, antioxidantand residual catalyst. Catalyst activity is reported as kilograms ofpolymer per mmol transition metal compound per hour of reaction time(kg/mmol*hr). Small scale ethylene/ENB copolymerization runs aresummarized in Table 1.

Polymer Characterization

For analytical testing, polymer sample solutions were prepared bydissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity fromSigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%from Aldrich) at 165° C. in a shaker oven for approximately 3 hours. Thetypical concentration of polymer in solution was between 0.1 to 0.9mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples werecooled to 135° C. for testing.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816;6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409;6,454,947; 6,260,407; and 6,294,388; each of which is incorporatedherein by reference. Molecular weights (weight average molecular weight(Mw) and number average molecular weight (Mn)) and molecular weightdistribution (MWD=Mw/Mn), which is also sometimes referred to as thepolydispersity (PDI) of the polymer, were measured by Gel PermeationChromatography using a Symyx Technology GPC equipped with dualwavelength infrared detector and calibrated using polystyrene standards(Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw)between 580 and 3,039,000). Samples (250 μL of a polymer solution in TCBwere injected into the system) were run at an eluent flow rate of 2.0mL/minute (135° C. sample temperatures, 165° C. oven/columns) usingthree Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns inseries. No column spreading corrections were employed. Numericalanalyses were performed using Epoch® software available from SymyxTechnologies or Automation Studio software available from Freeslate. Themolecular weights obtained are relative to linear polystyrene standards.Molecular weight data is reported in Tables 1 under the headings Mn, Mwand PDI as defined above. Differential Scanning Calorimetry (DSC)measurements were performed on a TA-Q100 instrument to determine themelting point of the polymers. Samples were pre-annealed at 220° C. for15 minutes and then allowed to cool to room temperature overnight. Thesamples were then heated to 220° C. at a rate of 100° C./minute and thencooled at a rate of 50° C./minute. Melting points were collected duringthe heating period. The results are reported in the Table 1, T_(m) (°C.).

Wt % ENB was calculated using the T_(m) and the following equation:

Wt % ENB=(128.36−T _(m))/2.57

where T_(m) is the melting point (° C.) of the polymer as measured byDSC as described directly above. The equation was developed from acorrelation between wt % ENB measured via ¹H NMR and DSC measurements ofethylene-ENB copolymers ranging from 0.8 to 26.6 wt % ENB as determinedby ¹H NMR. ENB content of the polymers used in the calibration wasdetermined as follows: The ¹H solution NMR was performed on a 5 mm probeat a field of at least 500 MHz in tetrachloroethane-d2 solvent (or a80:20 v/v ortho-dichlorobenzene and C₆D₆ mixture) at 120° C. with a flipangle of 30°, 15 s delay and 512 transients. Signals were integrated andthe ENB weight percent was reported.For calculation of ENB:I_(major)=Integral of major ENB species from 5.2-5.4 ppmI_(minor)=Integral of minor ENB species from 4.6-5.12 ppmI_(eth)=(Integral of —CH₂— from 0-3 ppm)

total=(ENB+E)

total wt=(ENB*120+E*14)

Peak Assignments Intensity of species MOLE % WEIGHT % ENB ENB =I_(major) + I_(minor) ENB * 100/total ENB * 120 * 100/total wt Ethylene(E) E = (I_(eth) − 11 * ENB)/2 E * 100/total E * 14 * 100/total wt

Polymerization results are collected in Table 1 below. “Ex#” stands forexample number. Examples starting with a “C” are comparative examples.“Cat ID” identifies the pre-catalyst/compound used in the experiment.Corresponding numbers identifying the pre-catalyst are located above. Anasterisk next to the Cat ID number indicates that the pre-catalyst waspre-alkylated with 20 equivalents of TiBAl. “Yield” is polymer yield,and is not corrected for catalyst residue or antioxidant content.“Quench time (s)” is the actual duration of the polymerization run inseconds. If a polymerization quench time is less than the maximum timeset (30 min), then the polymerization ran until the set maximum value ofethylene uptake was reached. ENB conversion (%) was calculated from thegrams of ENB in the polymer times 100, divided by the gram of ENB addedto the reactor. The grams of ENB in the polymer was calculated from thecalculated ENB wt % in the polymer times the polymer yield in grams anddividing by 100. The density used for ENB was 0.893 g/ml.

TABLE 1 Ethylene-ENB copolymerization examples quench Activity Calc. ENBCat time yield (kg P/mmol Mn Mw Mz PDI Tm Calc. ENB conversion Ex# ID(s) (g) cat · hr) (g/mol) (g/mol) (g/mol) (Mw/Mn) (° C.) (wt %) (%)  112 33 0.099 135 151,093 433,041 1,240,264 2.87 89.3 15.2 33.7  2 12 260.099 171 138,242 423,640 1,305,830 3.06 97.8 11.9 26.4  3 12 40 0.097109 209,242 569,323 1,502,105 2.72 91.1 14.5 31.4  4 12 27 0.097 162132,155 390,119 1,092,133 2.95 94.2 13.3 28.8  5 14 31 0.099 144 150,089443,455 1,326,847 2.95 91.5 14.3 31.8  6 14 37 0.100 122 172,848 471,9331,323,577 2.73 92.6 13.9 31.1  7 14 32 0.098 138 171,601 472,5151,255,718 2.75 92.9 13.8 30.2  8 14 44 0.085 87 262,688 566,0531,381,921 2.15 88.0 15.7 29.9  9 14 37 0.116 141 287,772 1,021,5153,829,558 3.55 85.9 16.5 42.9 10 14 66 0.118 81 206,429 1,083,5044,634,392 5.25 91.3 14.4 38.2 11 14 33 0.107 145 220,122 529,3041,365,911 2.40 88.8 15.4 36.7 12 14 34 0.114 151 173,399 455,1411,097,208 2.62 85.4 16.7 42.6 13 19 30 0.121 181 377,161 1,318,7644,604,667 3.50 74.3 21.0 56.8 14 19 42 0.121 130 333,882 780,6111,635,358 2.34 71.0 22.3 60.4 15 19 40 0.119 134 311,937 694,5251,428,476 2.23 71.7 22.0 58.6 C1  2 70 0.095 61 347,076 1,082,1733,347,662 3.12 121.6 2.6 5.6 C2  2 319 0.057 8 804,276 1,481,6423,809,758 1.84 119.3 3.5 4.5 C3  2 82 0.103 57 377,623 738,988 1,518,2851.96 121.7 2.6 6.0 C4  2 45 0.087 87 200,702 478,129 1,158,721 2.38122.5 2.3 4.4 C5  2 58 0.088 68 209,575 490,504 1,255,389 2.34 122.0 2.54.9 C6  2 36 0.082 102 215,637 460,694 1,044,499 2.14 122.5 2.3 4.2 C7 2 38 0.081 96 201,649 488,385 1,233,020 2.42 122.6 2.2 4.1 C8 16 1730.047 12 667,181 1,090,619 1,992,120 1.63 119.0 3.6 3.8 C9 16 51 0.07364 479,435 932,874 1,910,821 1.95 119.8 3.3 5.4 C10 16 47 0.076 73333,096 750,027 1,700,794 2.25 121.6 2.6 4.5 C11 16 44 0.073 75 375,304750,308 1,495,978 2.00 121.2 2.8 4.6 C12  8* 1800 0.024 0.60 199,868392,603 911,025 1.96 115.7 4.9 2.6 C13  8* 1801 0.020 0.50 205,613366,867 774,935 1.78 114.9 5.2 2.3 C14  8* 1801 0.022 0.55 220,320406,282 986,649 1.84 115.9 4.8 2.4 C15  8* 1701 0.029 0.77 221,594400,677 852,111 1.81 116.2 4.7 3.1 C16  17* 1801 0.012 0.30 142,432310,087 825,692 2.18 122.7 2.2 0.6 C17  17* 1801 0.010 0.25 C18  17*1802 0.015 0.38 187,746 386,390 1,108,036 2.06 123.4 1.9 0.6 C19  17*1800 0.006 0.15 C20  5* 1464 0.022 0.68 272,598 507,927 1,205,764 1.86119.3 3.5 1.7 C21  5* 1801 0.027 0.68 277,425 523,298 1,219,566 1.89119.2 3.6 2.2 C22  5* 1800 0.032 0.80 296,734 544,121 1,263,615 1.83121.0 2.9 2.1 C23  5* 1546 0.033 0.96 268,623 537,167 1,344,362 2.00121.3 2.7 2.0 C24  6* 1801 0.005 0.12 C25  6* 1800 0.010 0.25 C26  6*1800 0.012 0.30 218,868 490,841 1,909,729 2.24 117.7 4.1 1.1 C27  6*1800 0.009 0.22 C28 20 49 0.071 65 201,733 405,763 1,049,372 2.01 122.82.2 3.4 C29 20 41 0.075 81 188,520 383,215 876,596 2.03 123.0 2.1 3.5C30 20 44 0.072 74 194,966 403,391 961,063 2.07 124.0 1.7 2.7 C31 20 440.071 72 175,538 396,669 1,048,595 2.26 123.5 1.9 3.0For all runs, 0.34 ml toluene and 4.6 ml isohexane was used.

The above data shows that the inventive catalysts are capable ofincorporating greater amounts of ENB versus the comparative catalystsgiven the same polymerization conditions. Additionally, ENB conversionfor the inventive catalysts ranged from 26-60% whereas conversion forthe comparative catalysts ranged from 0.6 to 5.4%.

Large Scale Polymerization Examples

The ethylene copolymers in Examples L1 to L8 were made in a continuousstirred-tank reactor system with a 1 liter Autoclave reactor. Thereactors were equipped with a stirrer, a water cooling/steam heatingelement with a temperature controller, and a pressure controller. Thereactor was maintained at a pressure in excess of the bubbling pointpressure of the reactant mixture to keep the reactants in the liquidphase. The reactors were operated liquid full. Solvents and monomerswere first purified over beds of alumina and molecular sieves.Purification columns were regenerated periodically whenever there wasevidence of lower activity of polymerization. All liquid feeds werepumped into the reactors by a Pulsa feed pump. All liquid flow rateswere controlled using Brooks mass flow controller. Ethylene wasdelivered as a gas solubilized in the chilled solvent/monomer mixture.The purified solvents and monomers were then chilled to about −7° C. bypassing through a chiller before being fed into the reactors through amanifold. Solvent and monomers were mixed in the manifold and fed intoreactor through a single tube. Similarly, activated catalyst solutionwas fed using an ISCO syringe pump. Catalyst and monomer contacts tookplace in the reactor.

The reactors were first prepared by continuously N₂ purging at a maximumallowed temperature, then pumping isohexane and scavenger solutionthrough the reactor system for at least one hour. Monomers and catalystsolutions were then fed into the reactor for polymerization. Once theactivity was established and the system reached equilibrium, the reactorwas lined out by continuing operation of the system under theestablished condition for a time period of at least five times of meanresidence time prior to sample collection. The polymer produced in thereactor exited through a back pressure control valve that reduced thepressure to atmospheric. This caused the unconverted monomers in thesolution to flash into a vapor phase which was vented from the top of aliquid vapor separator. The liquid phase, comprising mainly polymer andsolvent, was collected for polymer recovery. The collected samples werefirst air-dried in a hood to evaporate most of the solvent, and thendried in a vacuum oven at a temperature of about 90° C. for about 12hours. The vacuum oven dried samples were weighed to obtain yields. Allthe reactions were carried out at a gauge pressure of about 2.7 MPa.

Catalysts used wererac-cyclotetramethylenesilylene-bis[4,7-dimethylinden-1-yl]hafniumdimethyl (14),rac-cyclotetramethylenesilylene-bis[4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl]hafniumdimethyl (19) and comparativerac-cyclotetramethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafniumdimethyl (2) and the activator used was N,N-dimethylaniliniumtetrakis(heptafluoro-2-naphthyl)borate (available from AlbemarleCorporation). The metallocene catalysts were preactivated with theactivator at a molar ratio of 1:1 in 900 ml of toluene. All catalystsolutions were kept in an inert atmosphere. Tri-n-octylaluminum (TNOAL)solution (available from Sigma Aldrich, Milwaukee, Wis.) was furtherdiluted in isohexane and used as a scavenger. Scavenger feed rate wasadjusted to maximize the catalyst efficiency. The catalyst feed rate canbe adjusted to achieve the yield and monomer conversion. The detailedprocess condition and some analytical results are summarized in Table 2.

TABLE 2 Ethylene-propylene - ENB copolymerizations Example # L1 L2 L3 L4Polymerization temperature 120 120 120 120 (° C.) Ethylene feed rate(g/min) 6.79 6.79 6.79 6.79 Propylene feed rate (g/min) 6 6 6 6 ENB feedrate (g/min) 1.33 1.33 1.33 1.78 Isohexane feed rate (g/min) 82.7 82.782.7 82.7 Catalyst ID 14 14 19 19 Catalyst feed rate (mol/min) 5.538E−074.500E−07 1.980E−07 3.043E−07 Conversion (%) 80.9% 83.6% 48.9% 59.4% ML(mu) * * 40.1 34 MLRA (mu-sec) 210.2 192.1 MST (mu) 9.1 8.5 MST RA(mst-sec) 90.9 87.7 Mn_DRI (g/mol) 57,021 Mw_DRI (g/mol) 135,413 Mz_DRI(g/mol) 262,617 Mw/Mn 2.37 Mn_LS (g/mol) 67,985 Mw_LS (g/mol) 142,558Mz_LS (g/mol) 302,033 g'vis 0.872 Ethylene content (wt %) 73.87 70.78ENB (wt %) * * 6.76 8.48 ENB conversion (%) 35.4 36.1 Example # L5 L6 L7Comp. L8 Polymerization temperature 120 120 120 120 (° C.) Ethylene feedrate (g/min) 6.79 6.79 6.79 6.79 Propylene feed rate (g/min) 6 6 6 6 ENBfeed rate (g/min) 1.78 1.78 1.78 1.33 Isohexane feed rate (g/min) 82.782.7 82.7 82.7 Catalyst 19 19 19 2 Catalyst feed rate (mol/min)2.282E−07 1.521E−07 1.065E−07 3.300E−07 Conversion (%) 53.9% 54.0% 49.6%41.5% ML (mu) 58.8 69.8 74.6 2.4 MLRA (mu-sec) 444.2 662.7 847 MST (mu)15.3 19.1 21 MST RA (mst-sec) 180.3 268.1 330.8 Mn_DRI (g/mol) 64,99780,492 80,708 Mw_DRI (g/mol) 178,087 224,061 218,561 Mz_DRI (g/mol)354,917 498,295 444,450 Mw/Mn 2.74 2.78 2.71 Mn_LS (g/mol) 83,186102,132 93,956 Mw_LS (g/mol) 194,223 238,884 251,675 Mz_LS (g/mol)412,152 473,557 583,426 g'vis 0.873 0.835 0.84 Ethylene content (wt %)73.3 73.8 74.58 73.6 ENB (wt %) 8.36 8.21 8.01 1.27 ENB conversion (%)32.4 31.9 28.6 5.6 * Polymer produced was of lower molecular weight andsticky.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is not incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.Likewise whenever a composition, an element or a group of elements ispreceded with the transitional phrase “comprising”, it is understoodthat we also contemplate the same composition or group of elements withtransitional phrases “consisting essentially of,” “consisting of”,“selected from the group of consisting of,” or “is” preceding therecitation of the composition, element, or elements and vice versa.

1. A process for producing copolymers comprising ethylene, a C₃ to C₁₂alpha olefin, and a cyclic olefin monomer, said process comprisingcontacting ethylene, a C₃ to C₁₂ alpha-olefin, and a cyclic olefinmonomer, with activator and a metallocene catalyst compound representedby the formula (I):

where each R² and R³ is hydrogen; each R⁴ is independently a C₁-C₁₀alkyl; each R⁵, R⁶ and R⁷ is independently hydrogen, C₁-C₅₀ substitutedor unsubstituted hydrocarbyl, or C₁-C₅₀ substituted or unsubstitutedhalocarbyl; and R⁴ and R⁵, R⁵ and R⁶ and/or R⁶ and R⁷ may optionally bebonded together to form a ring structure; J is a bridging grouprepresented by the formula R^(a) ₂J, where J is C or Si, and each R^(a)is, independently, C₁ to C₂₀ substituted or unsubstituted hydrocarbyl,and the two R^(a) form a cyclic structure incorporating J and the cyclicstructure may be a saturated or partially saturated cyclic or fused ringsystem; and each X is a univalent anionic ligand, or two Xs are joinedand bound to the metal atom to form a metallocycle ring, or two Xs arejoined to form a chelating ligand, a diene ligand, or an alkylideneligand.
 2. The process of claim 1 wherein the conversion of cyclicolefin monomer is greater than 6% based on the weight of cyclic monomerused in the process and the weight of cyclic monomer incorporated intothe polymer.
 3. The process of claim 1 wherein the cyclic olefin monomercomprises one or more of cyclopentadiene, cyclooctadiene, norbornadiene,dicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene,tricyclo[4.2.1.0^(2,5)]nona-3,7-diene, or higher ring containingdiolefins with or without substituents at various ring positions.
 3. Theprocess of claim 1 wherein the cyclic olefin monomer isdicyclopentadiene, 5-ethylidene-2-norbornene,5-methylidene-2-norbornene, or 5-vinyl-2-norbornene.
 4. The process ofclaim 1 wherein R⁴ and R⁷ are, independently, a C₁ to C₁₀ alkyl, and R²,R³, R⁵ and R⁶ are hydrogen.
 5. The process of claim 1 wherein R⁴ and R⁷are, independently, selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and isomersthereof.
 6. The process of claim 1 wherein R⁴ and R⁷ are, independently,a C₁ to C₁₀ alkyl.
 7. The process of claim 1 wherein each X is,independently, selected from the group consisting of hydrocarbylradicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides,sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and acombination thereof, (two X's may form a part of a fused ring or a ringsystem).
 8. The process of claim 1 wherein J is represented by theformula:

wherein J′ is a carbon or silicon atom, x is 1, 2, 3, or 4, and each R′is, independently, hydrogen or C₁-C₁₀ hydrocarbyl.
 9. The process ofclaim 1 wherein J is cyclopentamethylenesilylene,cyclotetramethylenesilylene, cyclotrimethylenesilylene.
 10. The processof claim 1 wherein the metallocene catalyst compound is selected fromthe group consisting of:cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,cyclopentamethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,cyclotrimethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafniumdichloride,cyclopentamethylenesilylene-bis(4,7-dimethylinden-1-yl)hafniumdichloride, cyclotrimethylenesilylene-bis(4,7-dimethylinden-1-yl)hafniumdichloride,cyclotetramethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl,cyclopentamethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl,cyclotrimethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl,cyclotetramethylenesilylene-bis(4,7-diethylinden-1-yl)hafniumdichloride,cyclopentamethylenesilylene-bis(4,7-diethylinden-1-yl)hafniumdichloride, cyclotrimethylenesilylene-bis(4,7-diethylinden-1-yl)hafniumdichloride,cyclotetramethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafniumdimethyl,cyclopentamethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafniumdimethyl,cyclotrimethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafniumdimethyl,cyclotetramethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafniumdichloride,cyclopentamethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafniumdichloride,cyclotrimethylenesilylene-bis(4,8-dimethyl-1,2,3-trihydro-s-indacen-5-yl)hafniumdichloride; and any compound where the dimethyl in any of the compoundslisted above is replaced with diethyl, dipropyl, diphenyl, dibenzyl,difluoride, dibromide, or diiodide.
 11. The process of claim 1 whereinthe activator comprises alumoxane.
 12. The process of claim 1 whereinalumoxane is present at a molar ratio of aluminum to catalyst compoundtransition metal of 100:1 or more.
 13. The process of claim 1 whereinthe activator comprises a non-coordinating anion activator.
 14. Theprocess of claim 1 wherein activator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein Z is (L-H) or a reducible Lewis Acid, L is anneutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) isa non-coordinating anion having the charge d−; and d is an integer from1 to
 3. 15. The process of claim 1 wherein activator is represented bythe formula:(Z)_(d) ⁺(A^(d−)) wherein A^(d−) is a non-coordinating anion having thecharge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acidrepresented by the formula: (Ar₃C⁺), where Ar is aryl or arylsubstituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substitutedC₁ to C₄₀ hydrocarbyl.
 16. The process of claim 1 wherein the activatoris one or more of: N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B],trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropillium tetraphenylborate, triphenylcarbeniumtetraphenylborate, triphenylphosphonium tetraphenylborate,triethylsilylium tetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate,1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, andtriphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). 17.The process of claim 1 wherein the catalyst system is supported.
 18. Theprocess of claim 1 wherein the catalyst system is supported on silica.19. The process of claim 1 wherein the catalyst system comprises twocatalyst compounds at least one of which is represented by the formula(I).
 20. The process of claim 1 wherein the process occurs at atemperature of from about 0° C. to about 300° C., at a pressure in therange of from about 0.35 MPa to about 20 MPa, and at a time up to 300minutes.
 21. The process of claim 1 further comprising obtainingcopolymer having at least 50% allyl chain ends.
 22. The process of claim1 wherein the copolymer comprises from 1 to 80 mol % ethylene, from 0 to60 mol % propylene and from 1 to 40 mol % cyclic monomer.
 23. Theprocess of claim 1 wherein the copolymer comprises from 1 to 80 mol %ethylene, from 0 to 60 mol % propylene and from 1 to 40 mol %vinylnorbornene, norbornadiene, and or ethylidene norbornene.
 24. Theprocess of claim 1 wherein the copolymer hs having at least 50% allylchain ends and comprises from 1 to 80 mol % ethylene, from 0 to 60 mol %propylene and from 1 to 40 mol % vinylnorbornene, norbornadiene, and orethylidene norbornene.
 25. The process of claim 1 wherein R⁴ and R⁷ are,independently, a C₁ to C₁₀ alkyl, and R² and R³ are hydrogen, and R⁵ andR⁶ are C₁ to C₁₀ alkyl, and where R⁵ and R⁶ join to form a 5 memberedring structure.
 26. The process of claim 1 wherein R⁴ and R⁷ are,independently, selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and isomersthereof, and where R⁵ and R⁶ join to form a 5 membered ring structure.27. The process of claim 1 wherein R⁴ and R⁷ are, independently, a C₁ toC₁₀ alkyl, and where R⁵ and R⁶ join to form a 5 membered ring structure.28. The process of claim 1 wherein each R³ is hydrogen; each R⁴ isindependently a C₁-C₁₀ alkyl; each R² is independently hydrogen; each R⁷is independently C₁-C₁₀ alkyl; each R⁵ and R⁶ is independently hydrogen,C₁-C₅₀ substituted or unsubstituted hydrocarbyl, or C₁-C₅₀ substitutedor unsubstituted halocarbyl; and R⁴ and R⁵, R⁵ and R⁶ and/or R⁶ and R⁷may optionally be bonded together to form a ring structure; J is abridging group represented by the formula R^(a) ₂J, where J is C or Si,and each R^(a) is, independently, C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl, and the two R^(a) form a cyclic structure incorporating Jand the cyclic structure may be a saturated or partially saturatedcyclic or fused ring system; and each X is a univalent anionic ligand,or two Xs are joined and bound to the metal atom to form a metallocyclering, or two Xs are joined to form a chelating ligand, a diene ligand,or an alkylidene ligand.